JPWO2007026545A1 - Plasma discharge treatment apparatus and method for producing gas barrier film - Google Patents

Abstract

The present invention provides a method for producing a highly functional film with reduced surface failure and improved yield, and a production apparatus therefor. This manufacturing apparatus is a plasma discharge processing apparatus that performs plasma discharge processing on the surface of a substrate that is continuously transferred between a winder and an unwinder at atmospheric pressure or a pressure near the atmospheric pressure. The surface to be treated of the material is a plasma discharge treatment apparatus that is conveyed in a contactless manner other than a nip roller that separates the discharge portion from the outside. Further, the present invention provides a method for producing a gas barrier film having a high gas barrier property with reduced surface failure (cracking failure) at the time of forming the gas barrier thin film. The radius of curvature during conveyance on the side is 75 mm or more, and the radius of curvature of the opposite surface is 37.5 mm or more.

Description

  The present invention relates firstly to a plasma discharge treatment method and apparatus for forming a thin film on a substrate by plasma discharge treatment, and for modifying the surface of the substrate, and in particular for a long support, surface damage. High performance film useful for liquid crystal display, organic electroluminescence display, plasma display, etc. by forming a thin film on the base film and modifying the surface without causing deterioration of performance due to defects caused by wiping The present invention relates to a plasma discharge treatment method and a plasma discharge treatment apparatus suitable for manufacturing the substrate. In particular, among these high-performance film base materials, surface failure (cracking failure) at the time of gas barrier thin film formation in the manufacturing method of a gas barrier film that forms a gas barrier thin film on a base film using a plasma discharge treatment method ) Is reduced, and the present invention relates to a method for producing a gas barrier film having high gas barrier properties.

  First, the prior art regarding the plasma discharge processing method and the plasma discharge processing apparatus (configuration) suitable for manufacturing the base material of the first high-functional film will be described.

  In recent years, displays such as liquid crystal image display devices, organic electroluminescence displays, plasma displays have become large screens, the amount of high-functional films used for these has increased, and diversification of high-functional films has progressed. It is required to supply such a high-functional film in large quantities at a low cost to the market.

  In the conventional method, first, a base film is manufactured and prepared as an original roll, the original roll film is fed out, a necessary thin film is formed on the base film, surface treatment is performed, When laminating a number of functional thin films, it is necessary to transport the production line many times. With regard to the plasma discharge processing apparatus as well, a large number of guide rollers are usually installed on the production line, and the film forming surface such as a dancer roller and EPC roller and the surface modification surface are contacted many times (for example, Patent Document 1). As a result, minute scratches or the like due to contact are generated on the surface of the base material, and the yield rate is reduced at present.

  Next, a gas barrier film for forming a gas barrier thin film on a base film and a method for producing the same will be described below.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging articles that require blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

  Aluminum foil is widely used as a packaging material in such fields, but disposal after use has become a problem, and it is basically opaque and the contents can be confirmed from the outside. In addition, the display material is required to be transparent and cannot be applied at all.

  On the other hand, a resin film made of polyvinylidene chloride resin, a copolymer resin of vinylidene chloride and other polymers, or a material provided with gas barrier properties by coating these vinylidene chloride resins on polypropylene resin, polyester resin, or polyamide resin However, it is widely used as a packaging material. However, since chlorine gas is generated during the incineration process, it is a problem from the viewpoint of environmental protection. Can not be applied to the field where is required.

  In particular, transparent resin films, which have been applied to liquid crystal display elements, organic electroluminescence (hereinafter abbreviated as organic EL) elements, etc., have recently been required to be lighter and larger, and have long-term reliability and shape. In addition to the high demands such as high degree of freedom and the ability to display curved surfaces, film base materials such as transparent plastics have begun to be used in place of glass substrates that are heavy and easily broken. For example, JP-A-2-251429 and JP-A-6-124785 disclose examples using a polymer film as a substrate of an organic electroluminescence element.

  However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. For example, when used as a substrate of an organic electroluminescence element, if a base material with poor gas barrier properties is used, water vapor or air permeates and the organic film deteriorates, which becomes a factor that impairs light emission characteristics or durability. In addition, when a polymer substrate is used as a substrate for an electronic device, oxygen permeates the polymer substrate and permeates and diffuses into the electronic device, which deteriorates the device or is required in the electronic device. This causes a problem that the degree of vacuum cannot be maintained.

In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. As a gas barrier film used for a packaging material or a liquid crystal display element, a method of depositing silicon oxide on a plastic film (for example, see Patent Document 2) or a method of depositing aluminum oxide (for example, see Patent Document 3). ) And the like, but in any case, the water vapor barrier property is about ² g / m ² / day (JIS K 7129: 240 ° C., 90% RH), or 2 ml / m ² / day / atm (JIS K 7126: 20). At present, it has only an oxygen barrier property of about 90 ° RH. In recent years, due to the development of organic EL displays that require further gas barrier properties, large-sized liquid crystal displays, high-definition displays, etc., the gas barrier performance for film substrates is on the order of 10 ⁻³ g / m ² / day for water vapor barrier properties. The demand is increasing.

  As a method to meet these demands for high water vapor barrier properties, a gas barrier film with a structure in which a dense ceramic layer and a flexible polymer layer that relieves impact from the outside are alternately laminated is proposed. (For example, refer to Patent Document 4).

However, when a gas barrier thin film composed of, for example, an adhesion film, a ceramic film, a protective film, or the like is formed as a laminate on a plastic film having flexibility, the structure layer has low flexibility and stress. On the other hand, in a relatively fragile layer, the thin film is liable to crack or break during transportation. This is because a support roller (also referred to as a guide roller) that holds and transports a plastic film when transporting a plastic film on which a gas barrier constituent layer having a relatively fragile characteristic as described above is transported when a laminate is formed. In the case of a roller having a small radius of curvature (R) (that is, a roller having a small diameter), the plastic film in contact with the roller is subjected to strong tensile stress and compression, and as a result, a relatively formed film formed on the plastic film. It has been clarified that a fragile gas barrier constituting layer causes cracking and thin film breakage, and the gas barrier property is remarkably lowered, and an immediate improvement is desired.
JP 2003-171770 A Japanese Examined Patent Publication No. 53-12953 (Example) JP 58-217344 A (Example) US Pat. No. 6,268,695 (claims 1, 2-54 to 3-26)

  As described above, the first object of the present invention is that the production of the conventional high-functional film has many guide rollers in contact with the film-forming surface and the surface-modified surface in the production line. There are considerable issues in terms of quality and quality, etc., and efforts are being made to improve production, such as simplifying production methods, increasing yields, reducing costs, and improving quality. is there.

  The present invention has been made in view of the above situation, and the first object of the present invention is to minimize the number of rollers in contact with the film-forming surface and the surface-modified surface in the production of a high-performance film. Therefore, by simplifying the production method, plasma discharge treatment that can reduce surface failure due to minute scratches caused by contact on the surface of the substrate and increase yield and reduce costs An object of the present invention is to provide a method for producing a high-performance film and a plasma discharge treatment apparatus.

  The second object of the present invention has been made in view of the second background, and is a gas barrier film having a high gas barrier property with reduced surface failure (cracking failure) during gas barrier thin film formation. It is to provide a manufacturing method.

  In this way, the present invention provides a plasma discharge treatment apparatus capable of reducing surface failure in the production of a high-performance film by surface treatment of a substrate, and the production of a gas barrier film with reduced surface failure. A method is provided.

  The first object of the present invention is achieved by the following structures (1) to (10), and the second object is achieved by the following structures (11) to (15).

(1) A plasma discharge treatment apparatus that performs plasma discharge treatment on the surface of a substrate that is continuously transferred between a winder (winding shaft) and an unwinder (unwinding shaft) under atmospheric pressure or a pressure in the vicinity thereof. , Between the unwinders, at least one of the two electrodes formed of cylindrical electrodes, and at least two nip rollers using the cylindrical electrode as a backup roller, between the nip rollers, and between the two opposed electrodes A voltage is applied between the two electrodes facing each other, the discharge part formed, the means for supplying the reaction gas at or near the atmospheric pressure provided in the discharge part, the means for discharging the exhaust gas after the treatment, Means for applying,
Each having a plasma discharge treatment apparatus,
In the discharge part, the reaction gas is supplied from the means for supplying the reaction gas,
In the plasma discharge processing apparatus for applying a voltage between the two electrodes facing each other to generate a plasma discharge and performing a plasma discharge process on the surface of the substrate passing through the discharge part while being in contact with the cylindrical electrode,
A plasma discharge processing apparatus, wherein a roller that contacts the surface to be processed of the base material between the winder and the unwinder is constituted only by a nip roller on a cylindrical electrode.

  (2) The plasma discharge processing apparatus according to (1), wherein a cleaning roller is provided in contact with a portion outside the region constituting the discharge portion of the cylindrical electrode.

  (3) The plasma discharge processing apparatus according to (1) or (2), wherein at least one EPC (edge position control) sensor is attached.

  (4) The winder and unwinder can change roles, and the substrate can be transferred in the reverse direction. By removing the wound substrate and removing it again, it is continuously discharged in a reciprocating manner. The plasma discharge treatment apparatus according to any one of (1) to (3), wherein the treatment is possible.

  (5) The plasma discharge processing apparatus according to any one of (1) to (4), wherein torque control is directly performed in the winder and unwinder.

  (6) The plasma discharge treatment apparatus according to any one of (1) to (5), wherein there is a preheating zone of the base material before the discharge unit.

(7) A plasma discharge treatment apparatus for performing plasma discharge treatment on the surface of a substrate to be continuously transferred under atmospheric pressure or a pressure in the vicinity thereof, and is formed between at least a pair of opposed electrodes and the opposed electrodes. Having a discharge part,
The base material passes through the discharge part while being in contact with one electrode of the opposing electrode, and after being subjected to plasma discharge treatment in the discharge part, the other part of the opposing electrode is again provided to the discharge part. It is transferred while being in contact with the electrode, and has a folding transfer means for plasma discharge treatment,
A means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof between a base material that reciprocally passes through the discharge section and a means for discharging the exhaust gas after treatment;
And a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned.

(8) A plasma discharge treatment apparatus that performs plasma discharge treatment on the surface of a substrate that is continuously transferred under atmospheric pressure or a pressure in the vicinity thereof,
A plurality of discharge portions formed between a plurality of pairs of opposed electrodes and the respective opposed electrodes, wherein the substrate is in contact with one electrode of each of the opposed electrodes; After passing through the discharge portion, the plasma discharge treatment is performed, and then the discharge portion is transferred to the discharge portion while being in contact with the other electrode facing each other, and the folded transfer means for performing the plasma discharge treatment is provided. Each has
In each discharge part, between the base material that reciprocally passes through each discharge part, it has a means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof, and a means for discharging exhaust gas after treatment,
And it is a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned.

(9) A plasma discharge treatment apparatus that performs plasma discharge treatment on the surface of a substrate to be continuously transferred under atmospheric pressure or a pressure in the vicinity thereof,
Having a discharge part formed between a pair of opposing electrodes and the opposing electrodes;
The base material passes through the discharge part while being in contact with one electrode of the opposing electrode, and after being subjected to plasma discharge treatment in the discharge part, the other part of the opposing electrode is again provided to the discharge part. It is transferred while being in contact with the electrode, and has a folding transfer means for plasma discharge treatment,
A means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof between a base material that reciprocally passes through the discharge section and a means for discharging the exhaust gas after treatment;
And a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned.

  (10) The plasma discharge treatment apparatus according to any one of (7) to (9), wherein the opposing electrodes are rotating roll electrodes.

  (11) In a method for producing a gas barrier film in which at least one gas barrier thin film is formed by a plasma CVD method on a resin film having a curvature and continuously conveyed, the gas barrier thin film having at least one layer of the resin film is included. A gas barrier film having a radius of curvature during conveyance of the surface A of 75 mm or more and a curvature radius of a surface B opposite to the surface A across the resin film is 37.5 mm or more Production method.

  (12) The method for producing a gas barrier film according to (11), wherein the gas barrier thin film includes an adhesive film, a ceramic film, and a protective film from the resin film side.

  (13) The production of the gas barrier film according to (11) or (12), wherein the ceramic film is formed of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, or a mixture thereof. Method.

  (14) In the plasma CVD method, a gas containing a gas barrier thin film forming gas and a discharge gas is supplied to a discharge space under an atmospheric pressure or a pressure near the atmospheric pressure, and a high-frequency electric field is applied to the discharge space. The method according to any one of (11) to (13), wherein a gas barrier thin film is formed on the resin film by exposing the resin film to the excited gas. The manufacturing method of the gas-barrier film of description.

  (15) The gas barrier property according to any one of (11) to (14), wherein a transport tension when continuously transporting the resin film is 50 N / m or more and 200 N / m or less. A method for producing a film.

  For the first object, according to the configurations (1) to (10) of the present invention (claims 1 to 10), the number of rollers in contact with the film forming surface is set to a minimum number. The production system has been simplified, there are few scratches and defects on the film-forming surface or surface modification surface, etc., and the yield is improved, which is more advantageous in terms of cost, mass supply, and quality than before. A production apparatus capable of obtaining a functional film can be provided.

  Further, for the second object, the above-described configurations (11) to (15) of the present invention (claims 11 to 15) reduce the failure (cracking failure) when forming the gas barrier thin film. Thus, a method for producing a gas barrier film having a high gas barrier property can be provided.

It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of this invention. It is the schematic which shows another example of the plasma discharge processing apparatus of this invention. It is the schematic which shows an example of a plasma discharge treatment process. It is the schematic which shows an example of the plasma discharge processing process in the plasma discharge processing apparatus concerning this invention. It is the schematic which shows another example of the plasma discharge processing process in the plasma discharge processing apparatus concerning this invention. It is the schematic which shows an example of the plasma discharge processing apparatus of this invention which consists of a rotating roll electrode and the opposing square tube-type electrode. It is a schematic diagram which shows an example of the batch type production line of the gas barrier film which concerns on this invention. It is a schematic diagram which shows an example of the production line of the online system of the gas barrier film which has several thin film formation stations. It is a schematic diagram which shows another example of the production line of the online system of the gas barrier film which has a some thin film formation station. It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the jet system useful for this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the contact conveyance system which processes a base material between useful counter electrodes for this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the non-contact conveyance system which processes a base material between counter electrodes useful for this invention. It is a perspective view which shows an example of the structure of the electroconductive metal base material of the roll rotating electrode shown in FIG. 5, FIG. 6, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a rectangular tube type electrode, and the dielectric material coat | covered on it.

Explanation of symbols

71 Original winding 72 Heating member 72 'Remaining heat zone 73 Cylindrical electrode 74, 74' Electrode 75, 78 Nip roller 76, 79 Partition plate 100 Discharge part 711 Supply port 712 Discharge port 713 Tension meter 714 EPC sensor 715 Rubber roller 716 Adhesive roller 700 Unwinder ( Unwinding shaft)
701 Winder (winding shaft)
720 Voltage application means F Substrate G Reactive gas G ° Plasma state gas G ′ Gas after treatment 10A, 10B, 10C, 10D, 10E, 10F Roll electrode 10a, 10b, 10c Square tube electrode 811A, 811B, 811C, 811D Folding roller (U-turn roller)
14, 14A, 14B Non-contact conveyance device 200, 210 Nip roller 30, 30A, 30B, 30C Reaction gas supply unit 40, 40A, 40B, 40C Discharge port 80 Power supply 91 First power supply 92 Second power supply 93, 94 Filter 81, 82 Voltage supply means 100, 100A, 100B, 100C Discharge unit 2 Original winding roll 5 Take-up roll AR1 to AR7 Guide roller AR (surface contact roller)
BR1 to BR3 Guide roller BR (Back contact roller)
CS1, CS2, CS3, 10 Atmospheric pressure plasma discharge treatment device 11 First electrode 12 Second electrode 21 First power supply 22 Second power supply 300 Plasma discharge treatment device 32 Discharge space 35 Roll rotating electrode 35a Roll electrode 35A Metal base material 35B Dielectric 36 Square tube type fixed electrode group 400 Electric field applying means 41, 410 First power source 42, 420 Second power source 43 First filter 44 Second filter 500 Gas supply means 51 Gas generator 52 Air supply port 53 Air exhaust port 600 Electrode Temperature control means

  Next, the best mode for carrying out the present invention will be described, but the present invention is not limited to this.

  First, the plasma discharge treatment apparatus according to claims 1 to 6 (the configurations (1) to (6)) will be described.

  From the original roll wound up in a roll shape, the substrate that has been unwound is continuously subjected to surface modification treatment by atmospheric pressure plasma treatment, or a functional thin film is formed on the substrate to function. Manufacturing a substrate having a conductive thin film is performed in various forms in the manufacture of an antiglare film, an antireflection film, a gas barrier film, and the like. In these production lines, various treatments that are additionally (and inevitably) performed, for example, drying, such as drying, after the pretreatment of the treated base material and after the treatment, are taken up smoothly. In addition to the necessary rollers, such as dancer rollers for adjusting tension and EPC rollers for detecting film edges, a large number of guide rollers are installed and processed in order to perform in a limited space. These rollers contact the film-forming surface and the surface-modified surface of the film several times.

  The plasma discharge treatment apparatus according to any one of claims 1 to 6 of the present invention includes rollers such as all guide rollers other than the nip roller as rollers that contact the film forming surface and the surface modification surface. This is a plasma discharge processing apparatus in which only the nip roller is excluded and is the only roller in contact with the film forming surface.

  The material of the nip roller is not particularly limited, but is preferably a treated substrate or a material that does not easily damage the surface of the functional thin film formed on the substrate, preferably hard rubber, plastic, etc. For this, a plastic or rubber roller having a rubber hardness of 60 to 80 according to JIS K 6253-1997 is preferable.

  Atmospheric pressure plasma discharge treatment refers to the application of an electric field by introducing a thin film forming gas or a processing gas into a discharge space composed of a first electrode and a second electrode facing each other at atmospheric pressure or near atmospheric pressure. Then, the thin film forming gas or the processing gas is excited, and the substrate is exposed to the excited thin film forming gas, whereby a thin film is formed on the substrate or surface modification is performed.

  For example, as the thin film forming gas, a rare gas is contained as a discharge gas, and an organometallic compound such as alkoxysilane is contained as a raw material gas, which is introduced into a discharge space composed of a first electrode and a second electrode. By applying a high frequency potential between the first electrode and the second electrode, the thin film forming gas is excited, and the base film is exposed to the excited thin film forming gas, so that a ceramic thin film such as silicon oxide is deposited on the base material. It is formed.

  Under atmospheric pressure or pressure near atmospheric pressure is a pressure of 20 kPa to 200 kPa, and a more preferable pressure between electrodes to which a voltage is applied is 70 kPa to 140 kPa. Under these pressures, the thin film forming gas to be introduced and the reactive gas are variously changed to form thin films having various properties on the base film. Modification and the like can be performed.

  The details of the plasma discharge treatment will be described later, and the plasma discharge treatment apparatus according to claims 1 to 6 of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus according to claims 1 to 6 of the present invention.

  In the plasma discharge processing apparatus according to the present invention, the base film F fed from the original winding 71 wound around the winding core attached to the unwinder (unwinding shaft) 700 is heated so as to face the base. The member 72 enters the discharge unit 100 after passing through a preheat zone 72 ′ in which the base film is preheated.

  In a preferred embodiment, the preheat zone 72 'is attached before entering the discharge section. In the discharge part 100, the base film is subjected to plasma discharge treatment in a state of being held at about 90 ° C to 200 ° C, preferably about 100 ° C to 150 ° C. By providing, it is preferable to avoid deformation such as shrinkage of the substrate due to a rapid temperature rise. Incidentally, in order to make the temperature of the base film in the discharge part as close as possible in this preheating zone (preheating part), the master winding 71 may be further heated if necessary.

  As the heating member 72 for heating the substrate in the preheating zone, a plate-like electric heater, ceramic heater, sheathed heater or the like sandwiched with mica on both sides is preferably used, and the substrate film is radiated heat immediately before the discharge part. In order to be able to warm up, it is attached at a fixed interval (0.5 mm to 5 mm) so as not to be in direct contact with it in parallel. Moreover, it is preferable to have a temperature control mechanism.

  The discharge unit 100 is located between two nip rollers 75 and 78 disposed on the cylindrical electrode 73, and includes a space between the cylindrical electrode 73 and an electrode 74 (here, square) facing the cylindrical electrode 73, and backs up the cylindrical electrode. The base material F is partitioned by a nip roller 75 and a partition plate 76 on the carry-in side of the base material and a plasma discharge processing vessel 77 as a roller, and by a nip roller 78 and a partition plate 79 on the carry-out side. As the electrode rotates, it is conveyed in contact with the cylindrical electrode. Reference numerals 711 and 712 denote a reaction gas supply port (supply means) and a discharge port (discharge means) for discharging exhaust gas after processing, and supply a reaction gas (thin film forming gas or process gas) from the reaction gas supply port. However, a high-frequency potential is applied by the voltage applying means 720 between the first and second electrodes facing each other, that is, the cylindrical electrode 73 and the electrode 74 facing the first and second electrodes. Plasma discharge is generated in the part, a thin film is formed on the surface of the substrate film conveyed on the cylindrical electrode 73, and surface modification treatment is performed. The treated exhaust gas is discharged from the discharge port 712.

  The cylindrical electrode 73, the square counter electrode 74, and the like have a structure in which a dielectric is coated on a conductive metallic base material. That is, it is preferable that ceramics is thermally sprayed as a dielectric on a conductive metallic base material and sealed using an inorganic compound sealing material. The ceramic dielectric may be a single-walled coating with a thickness of about 1 mm. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metallic base material include titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, etc., a composite material of iron and ceramics, or a composite material of aluminum and ceramics. However, titanium metal or titanium alloy is particularly preferable.

  When the dielectric is provided on one of the electrodes, the distance between the opposing electrodes is the distance between the dielectric surfaces, and is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of performing uniform discharge. is there.

  Further, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (water or silicon oil or the like) can be circulated. For example, the metallic base material structure of the rectangular tube type electrode is a metallic pipe, which serves as a jacket so that the temperature during discharge can be adjusted.

In the atmospheric pressure plasma discharge processing apparatus of the present invention, the high-frequency voltage applied between the opposing electrodes is a high-frequency voltage exceeding 100 kHz and power (output density) of 1 W / cm ² or more is supplied, and the processing gas Is excited to generate plasma.

  In the present invention, the upper limit of the frequency of the high-frequency voltage applied between the electrodes is preferably 150 MHz or less, and more preferably 15 MHz or less. Moreover, as a lower limit of the frequency of a high frequency voltage, Preferably it is 200 kHz or more, More preferably, it is 800 kHz or more.

Further, the upper limit value of the power supplied between the electrodes is preferably 50 W / cm ² or less, more preferably 20 W / cm ² or less. The lower limit is preferably 1.2 W / cm 2 or more. The discharge area (cm2) refers to an area in a range where discharge occurs in the electrode.

  The value of the voltage applied to the application electrode from the high frequency power supply is appropriately determined. For example, the voltage is about 10 V to 10 kV / cm, and the power supply frequency is adjusted to over 100 kHz and 150 MHz or less as described above.

  As for the power supply method, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.

  In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage in a plasma discharge processing apparatus.

  In the present invention, the power source for applying a voltage to the applied electrode is not particularly limited, but a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (10 kHz), and Kasuga. Electric high frequency power supply (15 kHz), Shinko Electric high frequency power supply (50 kHz), HEIDEN Laboratory impulse high frequency power supply (100 kHz in continuous mode), Pearl Industrial high frequency power supply (200 kHz), Pearl Industrial high frequency power supply (800 kHz), Pearl Industrial A high-frequency power source (2 MHz) manufactured by Pearl Industries, a high-frequency power source manufactured by Pearl Industries (13.56 MHz), a high-frequency power source manufactured by Pearl Industries (27 MHz), a high-frequency power source manufactured by Pearl Industries (150 MHz), or the like can be used. Preferably, it is a high frequency power source of more than 100 kHz to 150 MHz, preferably a high frequency power source of 200 kHz to 150 MHz, particularly preferably 800 kHz to 15 MHz.

  Next, the substrate subjected to the plasma discharge treatment is conveyed to the outside from the discharge portion only by the surface to be treated being in contact with the nip roller 78 and directly attached to the winder (winding shaft) 701 as a roll on the winding core. It is wound up.

  The plasma discharge processing apparatus according to the present invention is characterized in that there is no roller in contact with the surface on which the thin film is formed or modified except for the nip roller in contact with the cylindrical electrode. The introduction of a roller for adjusting the tension of the roller, or the necessary roller group or the like may inevitably introduce a roller in contact with the modified surface, and is not used in the present invention.

  Therefore, it is preferable to use an elastic material for the nip roller using the cylindrical electrode as a backup roller, such as hard rubber, plastic, etc., more preferably 60-80 in terms of rubber hardness according to JIS K 6253-1997 standard. Of these, rubber and plastic rollers are preferred.

  In the present invention, it is preferable to perform direct torque control in the winder (winding shaft) and unwinder (unwinding shaft).

  Torque control in the winder and unwinder is controlled so that the conveyance tension of the base film is constant. For example, the torque of the winder is controlled so that the tension of the winder or the base film wound from the center of the winding core is constant. The preferred tension is preferably in the range of 50 to 500 ± 10 (N / m), and most preferably controlled in the range of about 100 ± 10 N / m.

  In FIG. 1, reference numeral 713 denotes a tension meter, which is installed on the support side or at both ends, and measures a minute displacement to measure the tension. By feeding forward the measured information to the rotation of the winding shaft, the tension is controlled to be constant (feed forward control). As the tension meter, a non-contact tensiometer is also preferable. For example, a tension meter that can measure tension in a non-contact manner by air pressure using an air turn bar that is supplied with air from a blower in a range of fine pressure to low pressure may be used ( For example, Bellmatic: non-contact web tension meter). Alternatively, the output of the torque motor may be converted and used.

  Any method may be used for the torque control of the winder (winding shaft) to keep the tension of the substrate to be wound up. For example, when the motor is driven to rotate the winder, This can be done by adjusting the voltage. Current control or control that changes the frequency by an inverter may be used.

  The plasma discharge processing apparatus according to the present invention is preferably provided with at least one EPC sensor (edge position control sensor). The EPC sensor is used to detect the edge of the substrate film with an air servo sensor or an optical sensor, and the movement of the edge in the width direction is detected. In FIG. 1, reference numeral 714 denotes the EPC sensor.

  The meandering correction at the time of transporting the long base film can be performed simply by appropriately correcting the position of the winder 101 in the width direction based on the information of the sensor.

  In order to perform meandering correction with high accuracy, a meandering correction device is preferably used. That is, the conveyance direction is controlled on the basis of the detected information so that the edge of the film or the center in the width direction becomes a constant conveyance position. Specifically, as the actuator, one or two guides are used. Correct the meandering by touching the roller and the flat expander roller with drive left and right (or up and down) with respect to the line direction, or install a small pair of pinch rollers on the left and right of the film (on the front and back of the film) They are installed one by one, and they are on both sides of the film), and the film is sandwiched and pulled to correct meandering (cross guider system). The principle of the meandering correction of these devices is that when the film is moving, for example, when trying to move to the left, the former method tilts the roller so that the film goes to the right, and the latter method uses the right set. This pinch roller is nipped and pulled to the right. These meandering prevention devices can be installed.

  Furthermore, it is preferable that the plasma discharge treatment apparatus of the present invention is provided with a cleaning roller in contact with a cylindrical electrode conveyed on the substrate film while in contact with the substrate film.

  The cleaning roller is installed in contact with the cylindrical electrode outside the area of the discharge portion. As the simplest form, as shown in FIG. 1, a rubber roller 715 is used. When the rubber roller is in contact with the cylindrical electrode (at a constant pressure) and rotates in accordance with the rotation of the cylindrical electrode, it has an effect of transferring and removing foreign matters such as dust, dust, and dust adhering to the cylindrical electrode onto the surface of the rubber roller. The rubber roller is preferably made of an elastic material rather than the nip roller having a JIS hardness in the range of 30 to 70.

  Foreign matter such as dust and dust adhering to the rubber roller is further transferred to an adhesive roller 716 having an adhesive surface that rotates in contact with the rubber roller. This is a roller or the like with a double-sided tape or the like attached to the surface, and the material is not limited. As an adhesive roller, for example, there is an adhesive roller manufactured by TEKNEK. After the rubber roller comes into contact with the web or the like to remove micron-level foreign matter, it is transferred to the adhesive roller so that the rubber roller is always in a clean state. keep. The pressure-sensitive adhesive tape can be used by appropriately replacing it before transferring dust and dust from the rubber (rubber) roller.

  As a cleaning method, other methods such as a cleaning blade or a combination thereof may be used regardless of the cleaning roller.

  By removing the foreign matter adhering to the surface of the cylindrical electrode by the cleaning roller, no foreign matter is mixed into the back surface (between the electrodes) of the base material in the discharge portion, and the plasma discharge process is performed uniformly.

  In the above example, the substrate film fed from the unwinder (unwinding shaft) 700 is subjected to a thin film formation or surface modification treatment by plasma discharge treatment, and then the winder (winding shaft) 701 has been surface-treated. The base film is wound into a roll shape, and the first plasma discharge treatment is completed. However, in a preferred embodiment of the present invention, the unwinder (unwinding shaft) 700 is now the winding shaft, and the winder (Winding shaft) 701 is the unwinding shaft, so that the substrate film is transported in the reverse direction and further subjected to plasma treatment such as surface treatment or thin film formation on the surface-treated substrate. Can do. It is also an advantage of this apparatus that plasma discharge treatment can be performed in such a reciprocating manner.

  For this reason, the unwinder (winding shaft) and the winder (winding shaft) have a gear configuration that can be switched in the reverse direction.

  As a result, for example, the production of a multi-layered film such as an adhesion film, a gas barrier film, and further an adhesion film and a gas barrier film changes the transport direction, selects the reaction gas, and sets the plasma discharge conditions for each process. Thus, with the plasma discharge processing apparatus according to the present invention, it is possible to sequentially perform target processing and thin film formation.

  In this way, several processes such as forming and laminating thin films over several layers using plasma discharge treatment, or continuously performing surface modification treatment after forming the thin film, must be performed continuously. In some cases, the plasma discharge treatment apparatus of the present invention is useful, and the thin film formation surface or surface is in the middle except that the unwinding process, thin film forming process or surface modification process, and winding process are continued by any number of treatments. This is advantageous in that there is no guide roller in contact with the modified surface, and a high-quality film free from foreign matter failure due to scratches or pressing on the surface can be obtained.

  Next, another example of the plasma discharge processing apparatus according to claims 1 to 6 of the present invention is shown in FIG. This differs in the structure of the discharge part.

  In this atmospheric pressure plasma discharge apparatus, the discharge portion is different from that shown in FIG. 1, and the discharge portion will be mainly described.

  The atmospheric pressure plasma discharge apparatus shown in FIG. 2 applies two or more electric fields having different frequencies to the discharge space, and applies an electric field obtained by superimposing a first high-frequency electric field and a second high-frequency electric field.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge start The relationship with the electric field strength IV is
V1 ≧ IV> V2
Alternatively, V1> IV ≧ V2 is satisfied, and the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By taking such a discharge condition, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. I can do it.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is possible to increase the plasma density by a high power density and form a dense and high-quality thin film.

  In the atmospheric pressure plasma discharge processing apparatus of FIG. 2, the base film F is fed out from the original winding 71 wound around the winding core attached to the unwinder (unwinding shaft) 700 in the same manner as in FIG. After passing through the preheating zone 72 ′ in which the base film is preliminarily heated by the heating member 72 arranged in this manner, the discharge member 100 is entered.

  In the discharge part 10 formed between the rectangular electrodes (second electrodes) 74 and 74 ′ facing the cylindrical electrode (first electrode) 73, the substrate F is subjected to plasma discharge treatment to form a thin film or surface modification treatment Is to do.

  In the discharge space 100 formed between the electrode (second electrode) 74 and 74 ′ facing the cylindrical electrode 73, the cylindrical electrode 73 is supplied with a first frequency ω 1, electric field strength V 1, and current I 1 from the first power source 41. And a second high frequency electric field of frequency ω2, electric field intensity V2, and current I2 is applied from the second power source 42 to the opposing rectangular counter electrodes (second electrodes) 74 and 74 ′. .

  A first filter 43 is installed between the cylindrical electrode 73 and the first power supply 41, and the first filter 43 facilitates the passage of current from the first power supply 41 to the first electrode, and the second power supply 42. Is designed so that the current from the second power source 42 does not easily pass through to the first power source. A second filter 44 is installed between the opposing electrodes (second electrodes) 74 and 74 ′ and the second power source 42, and the second filter 44 is connected from the second power source 42 to the second electrode. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.

  In the present invention, the cylindrical electrode 73 may be the second electrode, and the fixed counter electrodes 74 and 74 ′ may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The thin film forming gas G generated by a gas generator (not shown) is introduced into the plasma discharge processing vessel from the air supply port 711 while controlling the flow rate by a gas flow rate adjusting means (not shown).

  The conveyed base material F passes through the nip roller 75 and is transferred to the discharge portion formed between the cylindrical electrode 73 and the opposing electrodes 74 and 74 ′.

  During transfer, an electric field is applied from both the electrodes 74 and 74 ′ facing the cylindrical electrode 73 to generate discharge plasma between the electrodes (discharge space). The substrate F is in contact with the gas in the plasma state while being wound while being in contact with the cylindrical electrode 73 to form a thin film.

  The number of fixed electrodes is two here along the circumference of the cylindrical electrode, but a plurality of fixed electrodes may be provided. The discharge area of the electrode is represented by the sum of the areas of the surfaces of all the fixed electrodes facing the cylindrical electrode 3 facing the cylindrical electrode 3.

  The substrate F passes through the nip roller 78 and is wound up by a winder as in FIG.

  The treated exhaust gas after the discharge treatment is discharged from the exhaust port 712.

  During the thin film formation, to heat or cool the cylindrical electrode and the fixed electrode, the medium whose temperature is adjusted by the electrode temperature adjusting means is sent to both electrodes via piping by a liquid feed pump etc., and the temperature is adjusted from the inside of the electrode. Is preferred. Reference numerals 76 and 79 denote partition plates for partitioning the plasma discharge processing container from the outside world. Reference numerals 715 and 716 denote the same rubber rollers and adhesive rollers as those in the apparatus shown in FIG. 1, and constitute cleaning rollers.

  As described above, the cylindrical electrode 3 and the rectangular tube-shaped electrode 74 have a structure in which a dielectric is coated on a conductive metallic base material. Further, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (water or silicon oil or the like) can be circulated. For example, the metallic base material structure of the rectangular tube type electrode is a metallic pipe, which serves as a jacket so that the temperature during discharge can be adjusted.

  The electrodes are preferably those obtained by thermally spraying ceramics as a dielectric material on a conductive metallic base material and sealing with an inorganic compound sealing material. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  The conductive metallic base material is also a metal such as titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, etc., a composite material of iron and ceramics or a composite material of aluminum and ceramics, etc. Titanium metal or titanium alloy is particularly preferred.

  When the dielectric is provided on one of the electrodes, the distance between the opposing electrodes is the distance between the dielectric surfaces, and is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of performing uniform discharge. is there.

  The plasma discharge treatment vessel is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. In FIG. 1, it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above material.

As two high-frequency power sources installed in such an atmospheric pressure plasma discharge processing apparatus, as a first power source (high-frequency power source),
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl industry 400kHz CF-2000-400k etc. can be mentioned, and all can be used.

In addition, as the second power source (high frequency power source)
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150 MHz CF-2000-150M and the like can be mentioned, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in which discharge occurs between the electrodes.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  The waveform of the high frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  The substrate subjected to plasma discharge treatment at two frequencies in this way is then conveyed to the outside from the discharge portion only by the surface to be treated being in contact with the nip roller 78 as in the apparatus in FIG. In addition, the torque of the winder (winding shaft) 701 is directly controlled by feedforward control so that the conveyance tension is fixed by the tension meter 713, and the winding is wound around the winding core as a roll.

  As described above, the plasma discharge processing apparatus according to the present invention is characterized in that there is no roller in contact with the thin film formed or modified surface other than the nip roller in contact with the cylindrical electrode.

  If the plasma discharge treatment apparatus shown in FIG. 2 is set to provide a thin film forming gas supply port and an exhaust port in the discharge space formed by the respective electrodes and the cylindrical electrode for the fixed electrodes 74 and 74 ′, Different thin film formations and surface modification treatments can be performed continuously in the same processing vessel. In addition, as in the plasma discharge processing apparatus of FIG. 1, the processing can be performed in the opposite direction by changing the transport direction, and a plurality of films can be stacked or processed by reciprocating thin film formation or surface modification processing. Can be done sequentially.

  As the mixed gas used in the plasma discharge treatment according to the present invention, various gases can be used depending on purposes such as thin film formation and surface modification treatment.

  In the plasma discharge treatment, a discharge gas that is likely to be in a plasma state and a reactive gas are mixed, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  Mixing the above-mentioned discharge gas with various reactive gases, for example, mixing the reactive gas necessary for thin film formation, and supplying this to the plasma discharge device, thin film formation or surface modification Surface modification can be performed by mixing and supplying the necessary reactive gas.

  The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  For example, the raw material used for manufacture of a ceramic material film | membrane is demonstrated.

  Ceramic material film is a metal carbide, metal nitride, metal oxide, metal by selecting conditions such as organometallic compound, decomposition gas, decomposition temperature, input power, etc. as raw materials (also called raw materials) in plasma discharge treatment The composition of sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxide halides, metal nitride carbides, etc.) can be made differently.

  For example, when a silicon compound is used as a reactive gas as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  Such a raw material compound may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use it with a solvent.

  Examples of such organometallic compounds include silicon compounds such as silane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, silane, alkoxysilanes such as titanium methoxide, titanium ethoxy. , Titanium isopropoxide, etc., titanium compounds, zirconium n-propoxide, etc., zirconium compounds, aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, etc., aluminum compounds, other, diborane, tetraborane, etc., boron compounds , Tetraethyltin, tetramethyltin and the like, tin compounds, and other organometallic compounds such as antimony and zinc.

  Moreover, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia as a decomposition gas for decomposing a raw material gas containing these metals into a reactive gas to obtain an inorganic compound Gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc. I can do it.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A film can be formed by mixing the discharge gas and the reactive gas and supplying the mixture as a thin film forming (mixed) gas to a plasma discharge generator (plasma generator).

  A silicon oxide film can be obtained by using alkoxysilane such as TEOS (tetraethoxysilane) as the reactive gas, and silicon oxide thin films having various compositions and properties can be obtained depending on the decomposition gas and its plasma discharge conditions. It is done.

  Further, without using a metal compound, for example, by using a decomposition gas such as oxygen gas as a reactive gas together with a discharge gas, the substrate surface modification treatment can be performed, and an organic fluorine compound, particularly a fluorine atom Surface modification treatment such as hydrophobization of the substrate surface can also be performed using a silane compound or the like containing

  Further, it is possible to form a polymer thin film by containing an organic compound in the thin film forming gas and performing plasma polymerization on the substrate.

As the organic compound that is a raw material component of plasma polymerization to be contained in the thin film forming gas, a known organic compound such as a monomer or oligomer of a (meth) acrylic compound, an epoxy compound, or an oxetane compound can be used. Plasma discharge according to the present invention The material of the substrate to be processed by the processing apparatus is not particularly limited, but is selected depending on the intended use such as a thin film formed on the substrate or a surface modification treatment. For example, when a gas barrier layer is formed on a resin film in order to form a transparent substrate such as an organic EL element, the resin film is preferably transparent.

  As a base material, although a long plastic (resin) film, paper, a nonwoven fabric, etc. can be mentioned according to a use, a resin film is preferable and will not be specifically limited if it is a resin film.

  Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) A long film substrate such as a fluorine-based resin such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used. . Moreover, what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, can also be used as a resin film.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (manufactured by Teijin Limited), Konicatac of cellulose triacetate film Commercially available products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  The resin film listed above may be an unstretched film or a stretched film.

  The resin film is advantageously a long product wound up in a roll shape. The thickness of the resin film varies depending on the use of the product to be obtained or the intermediate medium, and thus cannot be defined unconditionally. For example, from various uses such as a gas barrier film that is used for transportation and packaging, 3 to 400 μm, Is preferably 10 to 200 μm, more preferably 6 to 30 μm.

  As described above, the plasma discharge treatment apparatus of the present invention forms, for example, a thin film made of the ceramic film, metal oxide film, or the like on these substrates, and forms a gas barrier film, an antireflection film, or the like, or a transparent conductive material. A film on which a functional thin film such as a film is formed can be obtained with high quality and efficiency, and the present invention also includes surface modification, such as hydrophilization treatment, hydrophobization treatment, and roughening treatment by plasma discharge treatment. This plasma discharge treatment apparatus can be performed with high quality and efficiency.

  Next, a plasma discharge processing apparatus according to claims 7 to 10, which is another means for achieving the first object of the present invention, will be described.

  The plasma discharge device described in claims 7 to 10 of the present invention is similar to the plasma discharge treatment device described in claims 1 to 6 from the unwinding step to the thin film forming step. (Equipment) or surface modification step (Equipment), and among all the steps that are continuous with the winding step (Equipment), the thin film forming surface or the surface during the transfer of the substrate from the unwinding step to the winding step There is no guide roller in contact with the surface modification surface other than the necessary nip roller or the like, particularly during the film forming process.

  In the present invention, thin film formation means that a thin film is deposited (deposited) on a substrate by a dry method using the atmospheric pressure plasma discharge treatment apparatus according to the present invention.

  FIG. 3 shows an example of a conventional plasma discharge processing apparatus described in Japanese Patent Application Laid-Open No. 2003-171770.

  Here, an unwinding process and a winding process in which the base material is unwound from the original winding roll are not shown, and a plasma discharge treatment process in which a container such as glass is shielded from the outside air is shown.

  FIG. 3 is a diagram schematically showing a plasma discharge treatment process in which a substrate is reciprocated using two opposing roll electrodes. The substrate F supplied from the unwinding step or the original winding roll first passes through the nip roller 200, is held in close contact with the roll electrode 10A, is subjected to plasma discharge treatment in the discharge unit 100, and then turned back (U-turn roller). ) 811A to 811D are held in close contact with the roll electrode 10B, and a second treatment is performed in the discharge unit 100. The reactive gas G is supplied from the reactive gas supply unit 30, and the processed gas G ′ is discharged from the discharge port 40. The treated substrate F is transferred along with the rotation of the roll electrode 10B, and is transferred to the winding process via the nip roller 210. In addition, 80 is a power supply, 81 and 82 are voltage supply means.

  The plasma discharge treatment process is a plasma discharge treatment apparatus having a pair of roll electrodes for reciprocating a substrate.

  However, in these plasma discharge processing apparatuses, the film-forming surface on the base material or the modified surface of the base material has a nip roller 200, 210 or folding roller (U-turn roller) 811A to 811D during the plasma discharge processing. Etc., it will come into contact with several rollers. In addition, after the plasma discharge treatment, some rollers exist for the reason of shielding the plasma discharge treatment step from the outside air before the winding step.

  The present invention is the plasma discharge processing apparatus in which, in the plasma discharge processing described above, the rollers that are in contact with the film forming surface and the surface modification surface of the base material are removed as much as possible except for necessary ones. Necessary rollers include a nip roller having a roll electrode such as 200 and 210 as a back roller, and a roller such as a turn-back roller (U-turn roller) that is not shown but is in contact with the discharge process. Is preferred.

  FIG. 4 shows an example of a plasma discharge processing apparatus according to claims 7 to 10 of the present invention.

  FIG. 4 is a schematic view schematically showing a plasma discharge treatment step of the plasma discharge treatment apparatus of the present invention, which is similarly processed by reciprocating the substrate using two opposing roll electrodes.

  After the substrate F supplied from the unwinding step or the original winding roll (not shown) enters the plasma discharge treatment step, the substrate F rotates through the nip roller 200 using the rotating roll electrode 10A as a backup roller. 10A is held in close contact and transferred, and plasma discharge treatment is performed in the discharge unit 100. After the plasma discharge treatment is performed, the transfer direction is changed by the transfer means composed of the non-contact transfer device 14 that supports the continuously running web as the gas is ejected from the discharge port from the discharge portion, and is turned back. This time, it is held in close contact with the rotating roll electrode 10B, transferred again to the discharge part 100, and subjected to plasma discharge treatment in the discharge part.

  The reactive gas G is supplied from the reactive gas supply unit 30, and the processed gas G ′ is discharged from the discharge port 40. The processed substrate F is transferred along with the rotation of the roll electrode 10B, is transferred in a different direction via the nip roller 210, and is transferred to a winding process outside the processing chamber. In addition, 80 power supplies, 81 and 82 are voltage supply means.

  Here, the transfer means includes a non-contact conveyance device 14 that supports a web that continuously travels when gas is ejected from a blow-out port. As these non-contact conveyance devices (floaters), for example, a cross section Is a cylindrical roll having a cross section of an ellipse, semi-ellipse, elliptical arc, semicircle, ellipse, arc, etc., and has a semi-elliptical cross-section structure air discharge part such as SUS-304 and aluminum on the roller surface, A SUS-304 wire is wound around the air discharge section at an appropriate pitch, a flange with a fixed shaft portion is prepared at both ends of the roller, and a hole for supplying compressed air is provided on one side or both sides of the fixed shaft portion. For example, Laura. As another method, a roller having an air discharge portion made of a punching metal can be used.

  With this structure, when air is supplied, the degree of floating of the web is averaged along the outer peripheral surface and does not contact the roller surface.

  By supplying air from the blower to the inside of the roller, the substrate to be transferred is floated by pressure within a range of 0.1 kPa to 10 kPa, and conveyed without contact. The supplied air pressure value is determined by the mass and tension of the film that is levitated. Normally, the film tension is selected stepwise in direct proportion to the tension, but the film tension is measured with a tension meter, and the internal pressure value and the pressure of the supplied air are adjusted accordingly. To control the gap. As these rollers, for example, an air turn bar made by Bellmatic is available.

  According to these methods, during the plasma discharge treatment in the conventional plasma discharge treatment apparatus shown in FIG. 3, the folding roller (U-turn roller) that passes in the transfer of the treated substrate—both of the substrate treatments The transfer is performed while contacting the surface that has been touched, and by making this a non-contact transfer device, the thin film formed on the substrate, the surface that has undergone the modification treatment, the failure of the surface, Scratches can be greatly reduced.

  The rotating roll electrodes 10A and 10B have a structure in which a dielectric is coated on a conductive metallic base material. That is, it is preferable that ceramics is thermally sprayed as a dielectric on a conductive metallic base material and sealed using an inorganic compound sealing material. The ceramic dielectric may be a single-walled coating with a thickness of about 1 mm. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metallic base material include titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, etc., a composite material of iron and ceramics, or a composite material of aluminum and ceramics. However, titanium metal or titanium alloy is particularly preferable.

  The distance between the opposing roll electrodes is the distance between the dielectric surfaces, and is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of uniform discharge.

  Further, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (water or silicon oil or the like) can be circulated. For example, it is preferable that the metallic base material structure of the rectangular tube type electrode is a metallic pipe, which becomes a jacket so that the temperature can be adjusted during discharge.

  Although omitted in FIG. 4, in a preferred embodiment, in the discharge unit 100, the substrate is subjected to plasma discharge treatment while being maintained at 90 ° C. to 200 ° C., preferably about 100 ° C. to 150 ° C. Therefore, it is preferable to avoid deformation such as shrinkage of the base material due to a rapid temperature rise by providing a preheating zone before entering the discharge portion in advance. Therefore, the remaining heat zone is preferably provided at a position where the remaining heat can be sufficiently maintained during the process of transferring the substrate, for example, immediately before the discharge treatment chamber having the discharge unit 100.

  As the heating member for heating the base material in the preheating zone, for example, a plate-shaped electric heater sandwiched with mica on both sides, a ceramic heater, a sheathed heater, or the like is preferably used, and the base material is radiated immediately before the discharge portion. In order to be able to be heated by heat, it is attached at a constant interval (0.5 mm to 5 mm) so as to be parallel to this and not to be in direct contact. Moreover, it is preferable to have a temperature control mechanism.

  Moreover, in order to make the temperature as close as possible to the temperature of the base material in the discharge part in this preheating zone (preheating part), if necessary, the original winding roll on the unwinding shaft may be further heated.

Also in the atmospheric pressure plasma discharge treatment apparatus according to claims 7 to 10 of the present invention, the high-frequency voltage applied between the opposing electrodes is a high-frequency voltage exceeding 100 kHz and 1 W / cm ^2. The above power (power density) is supplied, and the processing gas is excited to generate plasma.

  Moreover, the upper limit of the frequency of the high frequency voltage applied between electrodes becomes like this. Preferably it is 150 MHz or less, More preferably, it is 15 MHz or less. Moreover, as a lower limit of the frequency of a high frequency voltage, Preferably it is 200 kHz or more, More preferably, it is 800 kHz or more.

Further, the upper limit value of the power supplied between the electrodes is preferably 50 W / cm ² or less, more preferably 20 W / cm ² or less. The lower limit is preferably 1.2 W / cm ² or more. The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

  The value of the voltage applied to the application electrode from the high frequency power supply is appropriately determined. For example, the voltage is about 10 V to 10 kV / cm, and the power supply frequency is adjusted to over 100 kHz and 150 MHz or less as described above.

  As for the power supply method, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.

  Also in the atmospheric pressure plasma discharge processing apparatus according to claims 7 to 10, it is necessary to apply an electrode capable of maintaining a uniform glow discharge state by applying such a voltage to the plasma discharge processing apparatus. There is.

  The power source for applying a voltage to the electrode is not particularly limited, but a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (10 kHz), and a high frequency power source manufactured by Kasuga Electric (15 kHz ), Shinko Electric High Frequency Power Supply (50 kHz), Heiden Institute Impulse High Frequency Power Supply (100 kHz in continuous mode), Pearl Industrial High Frequency Power Supply (200 kHz), Pearl Industrial High Frequency Power Supply (800 kHz), Pearl Industrial High Frequency Power Supply (2 MHz) A high frequency power source (13.56 MHz) manufactured by Pearl Industry, a high frequency power source (27 MHz) manufactured by Pearl Industry, a high frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be used as described above. Preferably, it is a high frequency power source of more than 100 kHz to 150 MHz, preferably a high frequency power source of 200 kHz to 150 MHz, particularly preferably 800 kHz to 15 MHz.

  In the plasma discharge processing apparatus according to claims 7 to 10, it is better that the number of rollers in contact with the surface on which the thin film is formed on the substrate or the surface of the modified substrate is smaller. For example, the introduction of a roller for adjusting the conveying tension requires the introduction of another group of rollers, which may result in a roller in contact with the modified surface, and may not be used in the present invention. preferable.

  For this reason, in the plasma discharge treatment apparatus according to claims 7 to 10, the winder (winding shaft) and the unwinder (unwinding shaft) are directly connected in unwinding and winding the substrate. It is preferable to perform torque control.

  The torque control of the winder and unwinder is controlled so that the conveyance tension of the substrate is constant. For example, the tension of the substrate wound by the winder (winding shaft) is preferably in the range of 50 ± 10 (N / m), preferably in the range of about 100 ± 10 (N / m). It is controlled to be constant.

  Therefore, a tension meter is installed on the support side or both ends, etc., on the take-up side (because it is alternated so that the take-up shaft or the unwind shaft is both), and the tension is measured by measuring a slight displacement. Then, the measured information is fed forward to the winding shaft torque so as to control the tension to be constant (feed forward control). As the tension meter, a non-contact tension meter is also preferable. For example, a tension meter that floats the film by air pressure using an air turn bar supplied with air from a blower in the range of fine pressure to low pressure and can measure tension without contact. (For example, manufactured by Bellmatic: non-contact web tension meter). Further, the tension may be controlled by converting the output of the torque motor into a tension.

  Any method may be used for torque control in the winder (winding shaft). For example, when the winder rotation is driven by a motor, the torque control of the motor can be performed by adjusting the voltage.

  Similarly to the above, the plasma discharge processing apparatus according to the present invention, of course, uses at least one EPC sensor (edge position control sensor), and a meandering correction apparatus for accurately performing meandering correction. It is preferable.

  It is also preferable that a cleaning roller similar to the above is provided in contact with each roll electrode conveyed on the substrate while in contact therewith.

  In addition, other types such as a cleaning blade or a combination thereof may be used regardless of the cleaning roller.

  In the above apparatus, it is possible to reverse the roles of the unwinder and the winder, reverse the direction of transport of the base material, and perform another surface treatment or plasma discharge treatment such as thin film formation on the surface-treated base material. it can. It is also an advantage of this apparatus that plasma discharge treatment can be performed in such a reciprocating manner. For this reason, it is preferable that the unwinding and winding shafts have a gear configuration in which the rotation in the reverse direction can be switched.

  Next, another example of the plasma discharge treatment apparatus described in claims 7 to 10 in which the plasma discharge treatment step is different from that shown in FIG. 4 will be described.

  The plasma discharge treatment step shown in FIG. 5 applies two or more electric fields having different frequencies to the discharge space, and applies an electric field obtained by superimposing the first high-frequency electric field and the second high-frequency electric field.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge The relationship with the starting electric field strength IV is
V1 ≧ IV> V2
Alternatively, V1> IV ≧ V2 is satisfied, and the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By taking such a discharge condition, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. I can do it.

  When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field intensity IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field intensity is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is possible to increase the plasma density by a high power density and form a dense and high-quality thin film.

  In the atmospheric pressure plasma discharge treatment apparatus of FIG. 5 as well as FIG. 4, the unwinding process and the winding process are not shown, but the substrate unrolled from the roll base material winding and transported to the discharge treatment process is not shown. The material F passes through the nip roller 200, is held by the rotating roll electrode 10A, is transported in close contact, and is subjected to plasma discharge processing in the discharge unit 100A (reactive gas G is supplied from the reactive gas supply unit 30A and processed) The subsequent gas G ′ is discharged from the discharge port 40A.) After that, the non-contact transfer device 14A that supports the continuously running web by further discharging gas from the discharge port 100A from the discharge port. Is transferred to the transfer means, and thus the surface is transported along the curved surface without contact, and again, this time, it is held by the rotating roll electrode 10B and is in close contact with it. Is fed, are transferred again to the discharge section 100A, it receives the second time of the plasma discharge treatment in the discharge unit.

  The treated base material F is further transferred along with its rotation on the roll electrode 10B, and the back surface thereof is brought into contact with the guide roller 822A and conveyed, and is then held and conveyed by the next roll electrode 10C. In the discharge unit 100B composed of 10D, the reaction gas supply unit 30B, the processed gas discharge port 40B, and the like are the same. However, after the plasma discharge process is performed once, the non-contact transfer device 14B further performs the transfer direction. Is returned to the discharge unit 100B together with the roll electrode 10D, and undergoes a plasma discharge treatment in a reciprocating manner.

  Similarly, in the example of FIG. 5, the same applies to the discharge unit 100 </ b> C that is transported in contact with the guide roller 822 </ b> B and formed from the roll electrodes 10 </ b> E and 10 </ b> F, the reactive gas supply unit 30 </ b> C, and the treated gas discharge port 40 </ b> C. In addition, the plasma discharge treatment is reciprocated by the contactless conveyance device 14C.

  Thereafter, the processed base material F passes through a nip roller 210 having a rotating roll electrode 10F as a backup roller, and then passes through a processing chamber separating the plasma discharge processing process from the outside to a winding process through a necessary nip roller. It is transported and wound up by a winder.

  As described above, the roll electrodes 10A, 10B, 10C, and 10D have a structure in which a dielectric is coated on a conductive metallic base material.

  The distance between the opposing roll electrodes is also preferably a distance between dielectric surfaces of 0.1 to 20 mm, particularly preferably 0.5 to 2 mm, from the viewpoint of uniform discharge.

  In addition, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated, It is preferable to be able to adjust the temperature during discharge, and this is also the same.

  The plasma discharge device in FIG. 5 performs a thin film formation or a surface modification process by performing plasma discharge processing on the base material F in a reciprocating manner in the discharge portions 100A to 100C formed between the roll electrodes.

  For example, in discharge spaces 100A to 100C formed between facing roll electrodes such as roll electrodes 10A and 10B and 10C and 10D, for example, the roll electrode 10A is supplied with frequency ω1, electric field strength V1, current I1 from the first power supply 91. A first high-frequency electric field is applied to the opposite roll electrode 10B from the second power source 92, and a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 is applied.

  The roll electrodes 10C and 10D and the roll electrodes 10E and 10F are also opposed to the roll electrodes 10C and 10F from the first power source 91 by the first high-frequency electric field having the frequency ω1, the electric field strength V1, and the current I1. A second high frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied from the second power source 92 to the roll electrode 10D and 10F.

  A first filter 43 is provided between the roll electrode 10A (first electrode) and the first power supply 91, and the first filter 93 facilitates the passage of current from the first power supply 91 to the first electrode. It is designed to ground the current from the second power source 92 and make it difficult to pass the current from the second power source 92 to the first power source. In addition, a second filter 94 is installed between the opposing roll electrode 10B (second electrode) and the second power source 92, and the second filter 94 has a current from the second power source 92 to the second electrode. Is designed to make it difficult to pass the current from the first power supply 91 to the second power supply.

  Similarly, between the roll electrodes 10C and 10D and between the roll electrodes 10E and 10F, the roll electrode 10C and the roll electrode 10E are used as the first electrode, and the roll electrode 10D and the roll electrode 10F are used as the second electrode. Similarly, as the electrodes, the first power source 91 and the filter 93 are connected to the first electrode, and the second power source 92 and the filter 94 are connected to the second electrode.

  In the present invention, the roll electrodes 10A, 10C, and 10E may be the second electrodes, and the opposing roll electrodes 10B, 10D, and 10F may be the first electrodes. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  A thin film forming gas G generated by a gas generator (not shown) is controlled in flow rate by a gas flow rate adjusting unit (not shown), and is supplied to the discharge units 100A to 100C from the reaction gas supply units 30A, 30B, and 30C, respectively. be introduced.

  During the transfer of the substrate, an electric field is applied between the two rotating roll electrodes facing each other, and discharge plasma is generated between the electrodes (discharge space). The base material F is wound while the back surface is in contact with each roll electrode, and comes into contact with the plasma state gas to form a thin film.

  The treated exhaust gas after the discharge treatment is discharged at the discharge ports 40A to 40C, respectively.

  The substrate subjected to the plasma discharge treatment in the apparatus is conveyed without contacting the surface of the substrate treated by the non-contact conveyance device during the plasma discharge treatment, and is passed through the nip roller 210 using the roll electrode 10F as a back roller. And sent to the winding process.

  In the apparatus shown in FIG. 5, three pairs of roll electrodes are arranged, but two pairs or more than two pairs may be installed.

  During plasma discharge treatment, in order to heat or cool each roll electrode, a medium whose temperature is adjusted by an electrode temperature adjusting means is sent to both electrodes via piping by a liquid feed pump or the like, and the temperature can be adjusted from the inside of the electrode. preferable.

  Each roll electrode has a structure in which a dielectric is coated on a conductive metallic base material as described above. The same applies to the dielectric and the metal matrix. Moreover, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated. Is preferred.

  In addition, FIG. 6 includes a rotating roll electrode and a rectangular tube electrode facing the roll electrode, and a first high frequency electric field and a second high frequency electric field having different frequencies are superimposed and applied between the electrodes. FIG. 6 shows an example of a plasma discharge treatment apparatus according to claims 7 to 10, which is different from the apparatus having the plasma discharge treatment step shown in FIG.

  Also in the atmospheric pressure plasma discharge processing apparatus shown in FIG. 6, the unwinding process and the winding process are not shown in the same manner as in FIG. The base material F fed out from the roll-shaped base material original winding enters the discharge processing chamber 31 via the nip roller 200 and the partition plate 220 via the non-contact conveyance device (floater) 14A, and is held by the rotating roll electrode 10A. In the discharge section 100A formed between the square tube electrode 10a that is transferred in close contact with each other, plasma discharge treatment is performed (the reaction gas G is supplied from the reaction gas supply section 30A, The gas G ′ is discharged from the discharge port 40A). After that, after exiting the discharge processing chamber through the nip roller 210 and the partition plate 230, the transport direction is reversed by another non-contact transport device (floater) 14B so that the processing surface does not come into contact with the reversing roller. Enter the discharge treatment chamber and receive the treatment continuously. This apparatus shows a plasma discharge processing apparatus in which three discharge processing chambers 31 each including a rotating roll electrode and three rectangular tube-shaped electrodes facing each roll electrode are continuous. Of course, one or more square tube electrodes may be arranged in each discharge treatment chamber.

  In any case, the non-contact conveying devices 14A to 14D that support the continuously running web by the gas being blown out from the blow-out port make the surface subjected to the plasma discharge treatment non-contact along the curved surface. In this example, plasma discharge processing is performed in three discharge processing chambers while being conveyed.

  Via the last non-contact conveyance device (floater), the discharge treatment surface is non-contact, and the treated substrate F is transferred to a winding process and wound by a winder.

  Further, in this apparatus, the non-contact transfer device is provided immediately before the plasma discharge treatment, and is also used as a preheating means for avoiding deformation such as shrinkage of the base material due to a rapid temperature rise by the plasma discharge treatment. I can do it.

  Note that the roll electrodes 10A, 10B, 10C and the rectangular tube type electrode shown in FIG. 6 also have a structure in which a dielectric is coated on a conductive metallic base material, as described above.

  The distance between the facing roll electrode and the rectangular tube type electrode is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of performing uniform discharge as the distance between the dielectric surfaces.

  Here, three fixed electrodes (in this case, rectangular tube electrodes) are arranged along the circumference of the cylindrical electrode, but one or more may be provided. The discharge area of the electrode is represented by the sum of the areas of the surfaces of all the fixed electrodes facing the rotating roll electrode facing the roll electrode. The discharge area can be increased by installing a plurality.

  In addition, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated, It is preferable to be able to adjust the temperature during discharge, and this is also the same.

  The plasma discharge apparatus in FIG. 6 performs a plasma discharge process on the base material F to perform a thin film formation or a surface modification process in the discharge portions 100A to 100C formed between the roll electrodes and the rectangular tube type electrodes. is there.

  Each roll electrode is a first electrode, and a square tube electrode is a second electrode. Between the roll electrode 10A and the square tube electrode 10a, for example, the roll electrode 10A is supplied with frequency ω1, electric field strength V1, current from the first power source 91. A first high-frequency electric field of I1 is applied, and a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 is applied from the second power source 92 to the opposing rectangular tube electrode 10a.

  A first filter 93 is installed between the roll electrode 10A (first electrode) and the first power source 91, and the first filter 93 facilitates the passage of current from the first power source 91 to the first electrode. It is designed to ground the current from the second power source 92 and make it difficult to pass the current from the second power source 92 to the first power source. Further, a second filter 94 is installed between the opposing rectangular tube electrode 10a (second electrode) and the second power source 92, and the second filter 94 is connected from the second power source 92 to the second electrode. It is designed so that the current from the first power supply 91 is grounded and the current from the first power supply 91 to the second power supply is difficult to pass.

  Similarly, between the roll electrode 10B and the rectangular tube electrode 10b, and between the roll electrodes 10C and 10c, the roll electrode 10B and the roll electrode 10C are the first electrodes, and the rectangular tube electrodes 10b and 10c. Similarly, the first power source 91 and the filter 93 are connected to the second electrode, and the second power source 92 and the filter 94 are connected to the second electrode.

  Further, the first electrode and the second electrode may be a square tube electrode and a rotating roll electrode, respectively, as in the case of FIG. In any case, the first power source is connected to the first electrode, the second power source is connected to the second electrode, and the first power source has higher high-frequency electric field strength than the second power source (V1> V2), The current is preferably I1 <I2, and the current value of the first and second high frequency electric fields is the same as in FIG.

As two high-frequency power sources installed in the atmospheric pressure plasma discharge processing apparatus as shown in FIGS. 5 and 6, as a first power source (high-frequency power source),
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl industry 400kHz CF-2000-400k etc. can be mentioned, and all can be used.

In addition, as the second power source (high frequency power source)
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150 MHz CF-2000-150M and the like can be mentioned, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in which discharge occurs between the electrodes.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  The waveform of the high frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  In the present invention, although not shown, a storage container for blocking the plasma discharge processing step as shown in FIG. 4 or 5 from the outside, and a storage container constituting the discharge processing chamber in FIG. Pyrex (registered trademark) glass processing containers and the like are preferably used, but it is also possible to use metal if insulation from the electrodes can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to obtain insulation. In FIG. 4 or 5, it is preferable that the plasma discharge treatment step is covered with an object made of the material as described above, including both side surfaces (up to the vicinity of the substrate surface) of both electrodes.

  In the apparatus having the plasma discharge treatment step shown in FIG. 5 and FIG. 6, it is assumed that the potential supplied from each power source can be independently applied to each roll electrode or square tube electrode, and each discharge space is provided. In addition, if different mixed gas supply ports and exhaust ports are provided, thin film formation under different conditions and surface modification treatment can be performed continuously in the same processing vessel. . In addition, the processing can be performed even if the conveyance direction of the substrate is changed, and a plurality of films can be stacked or processed sequentially by performing a thin film formation or a surface modification process in a reciprocating manner.

  Thus, the plasma discharge treatment apparatus of the present invention according to claims 7 to 10, that is, the unwinding step of unwinding the base material F from the original winding, and the plasma discharge treatment step by conveying from the unwinding. Transfer step until introduction, plasma discharge treatment step shown in FIG. 4, FIG. 5 or FIG. 6, and step of continuously conveying the treated substrate from the plasma discharge treatment step to the winding step, winding step In the plasma discharge treatment apparatus, the guide roller that contacts the treated surface of the base material is removed during the plasma discharge treatment step, and the nip roller necessary for the plasma discharge treatment step, and other plasma discharge treatment from the unwinding step. A nip roller used to block air accompanying the transfer of the web to the process, and a similar roller (a And by any) etc., is only the minimum required roller contact, it is possible to reduce failure due to contact of the guide roller or the like of the substrate surface.

  Therefore, as described above, the tension control by the dancer roller or the like is not preferable, and it is preferable that the torque control of the winder (winding shaft) is directly performed from the measurement by the tension meter as described above.

  As the mixed gas used in the plasma discharge processing apparatus according to claims 7 to 10, the thin film is the same as the mixed gas used in the plasma discharge processing apparatus according to claims 7 to 10. Various materials are used depending on purposes such as formation and surface modification treatment.

  In the plasma discharge treatment, a discharge gas that tends to be in a plasma state and a reactive gas (raw material gas) are mixed and sent to a plasma discharge generator (discharge unit). As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  Mixing the above-mentioned discharge gas and various reactive gases, for example, mixing raw material gas necessary for thin film formation, and supplying this to the plasma discharge device, thin film formation and surface modification Can do.

  The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  For example, in the production of ceramic material films, metal carbides, metal nitrides, metal oxides, metals, etc. are selected by selecting conditions such as organometallic compounds, decomposition gases, decomposition temperatures, and input power as raw materials (also referred to as raw materials) The composition of sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxide halides, metal nitride carbides, etc.) can be made differently.

  For example, when a silicon compound is used as a reactive gas as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  Moreover, such a raw material compound may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use it with a solvent.

  Such a raw material compound is preferably an organometallic compound, and the raw material compound is selected according to the type of ceramic material film to be obtained, such as silicon oxide or titanium oxide.

Examples of silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, silane, alkoxysilanes, etc., and examples of titanium compounds include titanium methoxide, titanium ethoxide. , Titanium isopropoxide, etc., and aluminum compounds include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide,
Zirconium compounds such as zirconium n-propoxide, other diborane, tetraborane, etc., boron compounds, tetraethyltin, tetramethyltin, etc., tin compounds, and other organometallic compounds such as antimony, zinc, etc.

  Moreover, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia as a decomposition gas for decomposing a raw material gas containing these metals into a reactive gas to obtain an inorganic compound Gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc. I can do it.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A film can be formed by mixing the discharge gas and the reactive gas and supplying the mixture as a thin film forming (mixed) gas to a plasma discharge generator (plasma generator).

  For example, a silicon oxide film can be obtained by using alkoxysilane, for example, TEOS (tetraethoxysilane) as a reactive gas. Depending on the decomposition gas and its plasma discharge conditions, oxidation having various compositions and properties can be obtained. A silicon thin film is obtained.

  Further, without using a metal compound, for example, by using a decomposition gas such as oxygen gas as a reactive gas together with a discharge gas, the substrate surface modification treatment can be performed, and an organic fluorine compound, particularly a fluorine atom Surface modification treatment such as hydrophobization of the substrate surface can also be performed using a silane compound or the like containing

  Further, it is possible to form a polymer thin film by containing an organic compound in the thin film forming gas and performing plasma polymerization on the substrate.

As the organic compound that is a raw material component of plasma polymerization to be contained in the thin film forming gas, a known organic compound such as a monomer or oligomer of a (meth) acrylic compound, an epoxy compound, or an oxetane compound can be used. Plasma discharge according to the present invention The material of the substrate to be processed by the processing apparatus is not particularly limited, but is selected depending on the intended use such as a thin film formed on the substrate or a surface modification treatment. For example, when a gas barrier layer is formed on a resin film in order to form a transparent substrate such as an organic EL element, the resin film is preferably transparent.

  As a base material, although a long plastic (resin) film, paper, a nonwoven fabric, etc. can be mentioned according to a use, a resin film is preferable and will not be specifically limited if it is a resin film.

  Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) A long film substrate such as a fluorine-based resin such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used. . Moreover, what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, can also be used as a resin film.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (manufactured by Teijin Limited), Konicatac of cellulose triacetate film Commercially available products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  The resin film listed above may be an unstretched film or a stretched film.

  The resin film is advantageously a long product (5 m to 3000 m) wound up in a roll shape. The thickness of the resin film varies depending on the use of the product to be obtained or the intermediate medium, and thus cannot be defined unconditionally. For example, from various uses such as a gas barrier film that is used for transportation and packaging, 3 to 400 μm, Is preferably 10 to 200 μm, more preferably 50 to 150 μm.

  As described above, by using the plasma discharge treatment apparatus according to the present invention according to claims 7 to 10, a thin film made of, for example, the ceramic film, the metal oxide film or the like is formed on these substrates, and a gas barrier film , Anti-reflection films, etc., and films with functional thin films such as transparent conductive films can be obtained with high quality and efficiency. Hydrophilic treatment, hydrophobic treatment, and roughening by plasma discharge treatment Processing and surface modification can also be performed with high quality and efficiency by the plasma discharge processing apparatus of the present invention.

  Next, when a gas barrier film is produced by forming a gas barrier thin film on a substrate by plasma discharge treatment, which is a means for achieving the second object of the present invention, particularly crack failure is greatly reduced. The method for producing a gas barrier film described in claims 11 to 15 will be described.

  As for the gas barrier film, as described above and in detail later, an organic metal compound, decomposition gas, or the like, which is a raw material (also referred to as a raw material), is selected on a substrate by plasma CVD, and conditions such as decomposition temperature and input power Is selected, and an adhesive film, a ceramic film, a protective film (hereinafter, the above layers formed on the substrate are collectively referred to as a gas barrier layer) and the like are manufactured.

  Since these gas barrier layers formed on the substrate include a metal oxide thin film, a failure such as a crack is likely to occur during the formation of the thin film, and the gas barrier film according to any one of claims 11 to 15 By using the manufacturing method, reduction of cracks on the surface of the thin film, which is one of surface failures, is achieved.

  Hereinafter, the manufacturing method of the gas barrier film described in claims 11 to 15 of the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventors have found that in a method for producing a gas barrier film in which at least one gas barrier thin film is formed by a plasma CVD method on a resin film having a curvature and continuously conveyed, The curvature radius of the surface A having the gas barrier thin film of at least one layer of the resin film being conveyed is 75 mm or more, and the curvature radius of the surface B opposite to the surface A across the resin film is 37. The method for producing a gas barrier film characterized by being 5 mm or more has been found to be able to realize a method for producing a gas barrier film having a high gas barrier property by reducing failure (cracking failure) during gas barrier thin film formation, It is up to the present invention.

  Details of the present invention will be described below.

<< Method for producing gas barrier film >>
In the method for producing a gas barrier film of the present invention, when forming at least one gas barrier thin film on a resin film using a plasma CVD method, the surface A having at least one gas barrier thin film of the resin film is: The curvature radius at the time of conveyance is 75 mm or more, and the curvature radius of the surface B opposite to the surface A across the resin film is 37.5 mm or more.

  Here, the curvature radius of the surface A or the surface B refers to the curvature radius of the curved surface formed by the outer surface of each surface.

  That is, when continuously transporting a gas barrier film having a gas barrier thin film formed by a plasma CVD method on a resin film, the radius of curvature during transport of the surface A having the formed gas barrier thin film should be 75 mm or more. Thus, it is possible to efficiently suppress the breakdown of the formed thin film without applying an excessive compressive stress to the gas barrier thin film. Further, by setting the radius of curvature at the time of conveyance of the surface B (hereinafter also referred to as the back surface) opposite to the surface A having the formed gas barrier thin film to 37.5 mm or more, the formed gas barrier thin film It was possible to prevent the formation of cracks and the like in the formed thin film without applying excessive tensile stress.

  In the present invention, as a means for realizing the conditions specified above, even if it is a method of conveying by a contact method while being held by a guide roller having a predetermined diameter, or a non-contact conveying device (floater, (It is also referred to as an air loop), and the floater shape may be appropriately selected and conveyed without contact.

  The upper limit of the diameter of each guide roller used in the contact method is not particularly limited, but the guide roller that contacts the surface A side from the viewpoint of increasing the equipment size due to the increased roller diameter or realizing stable conveyance. The diameter of AR is preferably 150 mm or more and 2000 mm or less, and the diameter of the guide roller BR in contact with the surface B is preferably 75 mm or more and 1000 mm or less.

  FIG. 7 is a schematic view showing an example of a production line by a batch method of the gas barrier film according to the present invention.

  In FIG. 7, the base F that is a resin film (having a polymer layer if necessary) is fed from the laminated original roll 2, and the guide roller BR <b> 1 in contact with the back surface (surface B) of the resin film, It passes through guide rollers AR1 and AR2 that are in contact with the surface (surface A), and is sent to a thin film forming station CS equipped with an atmospheric pressure plasma discharge processing apparatus for forming a gas barrier thin film. Here, a gas G containing a gas barrier thin film forming compound is fed into a plasma discharge portion composed of a roll rotating electrode 35 and a square fixed electrode pair 36 to excite the gas, and gas barrier properties are formed on the resin film F. A thin film is formed. Next, the film is taken up by the take-up roller 5 through the guide rollers AR3 and AR4 and the guide roller BR2. In addition, as an atmospheric pressure plasma discharge processing apparatus, only the roll rotating electrode 35, the square fixed electrode 36, and the gas G are shown for convenience, and description of other necessary parts is omitted. The atmospheric pressure plasma discharge processing apparatus according to the present invention will be described in detail later.

  At this time, in the guide rollers AR3 and AR4 (guide rollers in contact with the surface A) through which the resin film on which the gas barrier thin film is formed passes, the roll diameter is 150 mm or more, and the guide roller BR2 (the guide roller in contact with the surface B) Then, the roll diameter shall be 75 mm or more. At this time, as a matter of course, the diameter of the take-up roll 5 is required to be 75 mm or more when the take-up roll 5 is taken up with the surface on which the gas barrier thin film is formed as shown in FIG. In the case of winding with the surface on which the conductive thin film is formed facing inside, it is necessary to be 150 mm or more.

  In the method described above, a method for producing a gas barrier film having a gas barrier thin film composed of a single layer on the resin film has been shown. For example, an adhesion film, a ceramic film, a protective film, and the like are laminated on the resin film. In the production of the gas barrier film, the adhesion layer is provided by the above method, and the take-up roller 5 is used again as the original roll 2. Similarly, after the ceramic film is formed in the second step and further wound, Then, a protective film is formed in the third step. When forming a laminated body by such a batch method, guide rollers AR1 to AR4 (surface A) through which a resin film on which a gas barrier thin film (for example, an adhesion film or a ceramic film) is formed pass in the second step and thereafter. All the guide rollers BR1 and BR2 (guide rollers in contact with the surface B) have a roll diameter of 75 mm or more.

  FIG. 8 is a schematic view showing an example of a production line by an online system for a gas barrier film having a plurality of thin film forming stations.

  In FIG. 8, the basic configuration is similar to that of FIG. 7, but three stations (atmospheric pressure plasma discharge treatment apparatuses) for forming a gas barrier thin film CS1 to CS3 are provided, for example, gas G1 is used in CS1. In this method, an adhesion film is formed and a protective film is formed on-line continuously using CS2 using a gas G2 and CS3 using a gas G3. At this time, the guide rollers BR1, BR2, and AR1, which are in contact with the base material F (resin film) on which no gas barrier thin film is formed, are not particularly limited with respect to their respective diameters, but at least one gas barrier thin film is formed. The diameters of the guide rollers AR2 to AR7 in contact with the surface A of the resin film are 150 mm or more, and the guide roller BR3 in contact with the surface B is 75 mm or more.

  FIG. 9 is a schematic diagram showing another example of a production line using a gas barrier film having a plurality of thin film forming stations by an online system.

  The basic configuration of FIG. 9 is the same as that of FIG. 7, but a plurality of rectangular fixed electrode groups 36 are provided in the thin film forming station CS, and gases G1 to G3 having different compositions are supplied from each, for example, This is an on-line method for producing a gas barrier film in which an adhesion film is continuously formed using a gas G1, a ceramic film is formed using a gas G2, and a protective film is formed using a gas G3.

  Also in this case, regarding the guide rollers BR1, AR1, and AR1, which are in contact with the base material F (resin film) on which no gas barrier thin film is formed, there is no particular limitation regarding the diameter, but a gas barrier laminate was formed. The diameters of the guide rollers AR3 and AR4 in contact with the surface A of the subsequent resin film are 150 mm or more, and the guide roller BR2 in contact with the surface B is 75 mm or more.

  Moreover, in the manufacturing process of the gas barrier film of the present invention, the transport tension when continuously transporting the resin film is 50 N / m or more and 200 N / m or less, so that the formed gas barrier thin film is cracked or broken. It is preferable from the viewpoint of preventing and stable conveyance, and more preferably 80 N / m or more and 150 N / m or less. When the transport tension is 50 N / m or more, stable transportability can be obtained, and a uniform coating film can be formed. Moreover, if conveyance tension | tensile_strength is 200 N / m or less, an excessive distortion will not be given to the gas-barrier thin film formed on the resin film currently conveyed, and generation | occurrence | production of a crack and thin film destruction can be prevented.

<Gas barrier thin film>
Next, details of the gas barrier thin film according to the present invention will be described.

  The gas barrier thin film according to the present invention may be composed of at least one gas barrier thin film having gas barrier properties, but preferably has a laminate structure composed of two or more gas barrier thin films. Is preferably composed of an adhesive film, a ceramic film and a protective film from the resin film side, from the viewpoint of obtaining higher order water vapor barrier properties and oxygen barrier properties.

  In the configuration including the adhesion film, the ceramic film, and the protective film according to the present invention, the density of the ceramic film is preferably higher than the densities of the adhesion film and the protective film positioned above and below the ceramic film. By reducing the density of the adhesion film and the protective film from that of the ceramic film, the adhesion film and the protective film become slightly flexible and have a low filling degree, and when laminated with the ceramic film, the gas film has high density and high density. Stress can be relaxed by improving flexibility as compared with ceramic films. The adhesion film simultaneously has an action of relieving stress from the outside, improves adhesion between the ceramic film and the base material or a polymer film described later, improves bending resistance, and the protective film has stress from the outside. In addition, the dense ceramic film with high hardness is weak against external stress and easily breakable by bending, etc., for example, in the production of organic EL elements, the formation of a transparent conductive layer, etc. Post-process suitability can be imparted.

  The thickness of each of the adhesion film, the ceramic film layer, and the protective film according to the present invention (generally also referred to as a gas barrier layer) varies depending on the type and configuration of the material used, and is appropriately selected. It is preferably in the range of ˜5000 nm, and more preferably in the range of 1 to 2,000 nm. This is because if the thickness of the gas barrier layer is thinner than the above range, a uniform film cannot be obtained and it is difficult to obtain a barrier property against gas. In particular, the thickness of the ceramic film is preferably in the range of 0.1 to 5000 nm, more preferably in the range of 1 to 1000 nm. When the ceramic layer is thicker than the above range, it is difficult to maintain flexibility in the gas barrier film, and the gas barrier resin base material is cracked due to external factors such as bending and pulling after the film formation. It is because there is a risk of.

  The adhesion film is a layer that has a role of stress relaxation and improves adhesion and adhesion to the substrate. The film thickness of the adhesion film is preferably 1 to 500 nm, and more preferably 20 to 200 nm. The protective film is preferably 1 to 1000 nm, more preferably 100 to 800 nm as the thickness of the protective film for protecting the ceramic film.

  In the present invention, the composition of the gas barrier layer is not particularly limited as long as each thin film prevents oxygen and water vapor from permeating. Specifically, the gas barrier layer according to the present invention, that is, the adhesion film, the ceramic film, and the protective film are configured to contain the same ceramic material, and the ceramic material includes metal carbide, metal nitride, metal oxide, and metal sulfide. And metal halides, and mixtures thereof (metal oxynitrides, metal oxide halides, metal nitride carbides, etc.). Of these, metal oxides, metal oxynitrides, and metal nitrides are preferable. Specifically, silicon oxide, aluminum oxide, silicon nitride, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, Preferred examples include tin oxide, and preferably silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, or a mixture thereof.

  As a method for sequentially forming these adhesion film, ceramic film, and protective film on a substrate, it is characterized by using a plasma CVD method, and in particular, a plasma CVD method at or near atmospheric pressure described later is used. It is preferable to use it.

  The gas barrier layer according to the present invention is preferably composed of a plurality of films containing the same composition and having different densities from the viewpoints of adhesion and stable thin film formation. This is because even if it is the same composition, depending on the manufacturing conditions, the type of raw materials used, the ratio, etc., the degree of filling of ceramic particles, the difference in the amount of mixed impurity particles, etc., resulting in the physical properties accompanying it, for example, It depends on the density etc.

  The adhesion film and the protective film according to the present invention are films containing the same composition as the ceramic layer, and have a film density smaller than that of the ceramic film. A film having a density of 95% or less is preferable. These layers are low in density and do not have the ability to block water vapor as much as the ceramic layers, but they are flexible and serve as stress relaxation layers and adhesion layers or protective layers while being films containing the same composition. Can be fulfilled.

  In the present invention, the laminated film constituting the gas barrier layer is preferably formed by an atmospheric pressure plasma CVD method. Therefore, in the present invention, at least one or all of the adhesion film, ceramic film and protective film according to the present invention are formed into a thin film containing a source gas and a discharge gas in the discharge space under atmospheric pressure or a pressure in the vicinity thereof. A gas is supplied and a high frequency electric field is applied to the discharge space to excite the gas. By exposing the resin base material on which the gas barrier layer is to be formed to the excited gas, a thin film is formed on the base material. It is preferable to form by using the atmospheric pressure plasma CVD method.

  The vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable in order to obtain a good effect described in the present invention.

  In the thin film formation by the atmospheric pressure plasma CVD method as described above, the thin film forming gas mainly includes a raw material gas for forming a thin film, a decomposition gas and a plasma for decomposing the raw material gas to obtain a thin film forming compound. It is comprised from the discharge gas for setting it into a state.

  In the present invention, it is preferable that the adhesion film, the ceramic film, and the protective film are formed of substantially the same composition on the resin film. For example, in the thin film formation by the atmospheric pressure plasma CVD method, the thin film formed of the same composition. It is preferable to use a thin film forming gas for forming each of the above, which makes it possible to produce a very stable production without contamination of impurities, and to maintain good adhesion without deterioration even when stored in a harsh environment. A gas barrier film having excellent transparency and gas barrier resistance can be obtained.

  In the gas barrier film according to the present invention, a method for forming an adhesion film, a ceramic film, and a protective film having a desired configuration is not particularly limited, but an optimal raw material is selected, and a raw material gas, a decomposition gas, and a discharge are selected. It is preferable to appropriately select the gas composition ratio, the supply rate of the thin film forming gas to the plasma discharge generator, the output conditions during the plasma discharge treatment, and the like.

  Next, components of the gas barrier film according to the present invention will be described.

<Adhesion film, ceramic film and protective film>
The raw materials used in the production of the adhesion film, ceramic film and protective film (hereinafter collectively referred to as gas barrier layer) according to the present invention will be described.

  In the gas barrier layer according to the present invention, in the plasma CVD method and the atmospheric pressure plasma CVD method, by selecting conditions such as an organic metal compound, a decomposition gas, a decomposition temperature, and an input power as a raw material (also referred to as a raw material), a metal carbide, The composition of metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides, metal nitride carbides, etc.) can be made differently.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Moreover, if a zinc compound is used as a raw material compound and carbon disulfide is used as the cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

As such an organometallic compound,
As silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, Diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethyl Amino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminoto Methylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris ( Dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3 -Disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltri Tylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane , Hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed and supplied to a plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. The ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, but the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  In the gas barrier layer according to the present invention, the inorganic compound contained in the gas barrier layer is preferably at least one selected from silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, and a mixture thereof, particularly water vapor or oxygen From the viewpoint of gas barrier properties such as gas barrier properties, light transmittance, and suitability for atmospheric pressure plasma CVD described later, silicon oxide is preferable.

  The inorganic compound according to the present invention can obtain, for example, a film containing at least one of O atoms and N atoms and Si atoms by further combining oxygen gas and nitrogen gas at a predetermined ratio with the organic silicon compound. .

  In order to obtain a stable gas barrier film whose gas barrier performance does not change even under severe conditions, the gas barrier layer according to the present invention, that is, among the adhesive film, ceramic film and protective film composed of the same composition, is particularly ceramic. The membrane preferably has a compressive stress of greater than 0 MPa and no greater than 20 MPa.

  A gas barrier film formed by a plasma CVD method, particularly an atmospheric pressure plasma CVD method, as compared with a sol-gel method, a vacuum deposition method, a sputtering method, or the like can form a film with a small internal stress and a small distortion.

  The ceramic film formed by these methods is therefore dense and high in density, and at the same time has low internal stress, meaning that the film is less distorted, smooth and average for deformation due to bending, etc. In order to mean strong, it is preferable that the ceramic film of the present invention is a film having a low compressive stress of more than 0 MPa and not more than 20 MPa.

  When the stress is too small, there may be a partial tensile stress, and the film is easily cracked or cracked, resulting in a non-durable film. When the stress is too large, the film is easily cracked.

<Polymer layer>
In the present invention, it is preferable to have a polymer film between the adhesion film and the resin film. This is formed for the purpose of improving the adhesion and adhesion between the adhesion layer and the resin film substrate among the gas barrier layers. Further, if a polymer film having a Tg higher than that of the resin film substrate is selected, an effect of suppressing expansion and contraction due to heat can be obtained, which contributes to improvement of adhesion when exposed to more severe conditions.

  As a polymer film, it is a polymer film which exists in the range of 0.1-10 micrometers in thickness, Preferably it is the range of 0.5-10 micrometers.

  The polymer film is preferably a resin coating layer such as an acrylic resin, a polyester resin, or a urethane resin, and is easily formed by coating a corresponding resin solution on a resin substrate by a known method such as roll coating, gravure coating, dip coating, or the like. it can.

  In the present invention, these polymer layers are preferably formed from a thermosetting resin or an actinic radiation curable resin, and it is particularly preferable to form a cured resin layer using an ultraviolet curable resin. In addition, before forming these layers, it is preferable that the surface of the resin base material (film) is subjected to corona discharge treatment or glow discharge treatment.

  The cured resin layer is preferably a layer formed by polymerizing a component containing at least one monomer having an ethylenically unsaturated bond, and a resin formed by polymerizing a component containing a monomer having an ethylenically unsaturated bond As the layer, a layer formed by curing an actinic ray curable resin or a thermosetting resin is preferably used, and an actinic ray curable resin layer is particularly preferably used. Here, the actinic radiation curable resin layer refers to a layer mainly composed of a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams.

  Typical examples of the actinic radiation curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. For example, an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin, which are mainly composed of acrylic, are preferable.

  Specific examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

  In general, UV-curable acrylic urethane resins include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. And acrylate-based monomers such as 2-hydroxypropyl acrylate, which are easily formed by reaction with acrylate monomers having hydroxyl groups, such as those described in JP-A-59-151110. Can be used.

  Examples of UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. Those described can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Specific examples of these photoinitiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoreactive agent, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available UV curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sun Rad H-601 (manufactured by Sanyo Chemical Industries); SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (Grace Japan ( Alonix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.) and the like can be appropriately selected and used.

  These actinic radiation curable resin layers can be applied by a known method.

As a light source for curing the ultraviolet curable resin by a photocuring reaction, any light source that generates ultraviolet light can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on individual lamps, irradiation light amount 20~10000mJ / cm ² degree located in well, preferably 50~2000mJ / cm ^2. By using a sensitizer having an absorption maximum in the near-ultraviolet region to the visible light region, it can be efficiently formed.

  The organic solvent for the UV curable resin layer composition coating solution is appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other organic solvents, or mixed and used. it can. For example, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5%. It is preferable to use the organic solvent containing -80% by mass or more.

  The coating amount of the ultraviolet curable resin composition coating solution is suitably from 0.1 to 30 μm, preferably from 0.5 to 15 μm, as the wet film thickness. The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin. More preferred is ~ 2 minutes.

  Further, as the polymer film according to the present invention, a plasma polymerized film formed by using the atmospheric pressure plasma CVD method is a preferable polymer film. That is, in the atmospheric pressure plasma CVD method, at least one kind of organic compound is contained in the thin film forming gas, and the polymer film is formed by plasma polymerization of the organic compound.

  In the atmospheric pressure plasma CVD method, the thin film forming gas is composed of a discharge gas and raw material components, and an additive gas may be further used.

  As the organic compound which is a raw material component according to the present invention, a known organic compound can be used. Among them, an organic compound having at least one unsaturated bond or cyclic structure in the molecule is preferably used. In particular, a monomer or oligomer of a (meth) acrylic compound, an epoxy compound, or an oxetane compound can be preferably used. Particularly preferred is an acrylic or methacrylic compound or the like containing acryl as a main component.

  Although there is no limitation in particular as a useful (meth) acryl compound, The following compounds are mention | raise | lifted as a typical example. 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3-dioxane alcohol Of ε-caprolactone adduct, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or methacrylic acid esters obtained by replacing these acrylates with methacrylates, such as ethylene glycol diacrylate, triethylene glycol diacrylate , Pentaerythritol diacrylate, hydroquinone diacrylate, resorcindiak Rate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, ε-caprolactone adduct of neopentyl glycol hydroxypivalate Ε of diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate -Bifunctional acrylic acid esters such as caprolactone adduct, diglycidyl ether diacrylate of 1,6-hexanediol, or these acrylates Methacrylic acid esters instead of relate, such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, etc. The polyfunctional acrylic acid Ester acid or methacrylic acid or the like instead of these acrylate with methacrylate. The compounds mentioned as the actinic radiation curable resin are also included.

  The discharge gas is the same as in the case of the gas barrier layer, and includes nitrogen, rare gas, air, etc. As the rare gas, the 18th group element of the periodic table, specifically, helium, neon, argon, krypton In the present invention, the discharge gas is preferably nitrogen, argon, or helium, and more preferably nitrogen.

  In the plasma polymerization, the discharge gas amount is preferably 70 to 99.99% by volume with respect to the thin film forming gas amount supplied into the discharge space.

  Also in the plasma polymerization method, in addition to the raw material gas and discharge gas, an additive gas may be introduced to control the reaction and film quality, and hydrocarbons such as hydrogen, oxygen, nitrogen oxides, ammonia, methane, etc. Alcohols, organic acids, or moisture may be mixed in 0.001% to 30% by volume with respect to the gas.

<Resin film>
The resin film used as a base material in the gas barrier film according to the present invention is not particularly limited as long as it is a resin film that holds the gas barrier layer and can be continuously conveyed.

  Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) Fluorine-based resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a resin film.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (manufactured by Teijin Limited), Konicatac of cellulose triacetate film Commercially available products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  The resin film is preferably transparent. Since the resin film is transparent and the gas barrier layer formed on the resin film is also transparent, a transparent gas barrier film can be obtained, and thus a transparent substrate such as an organic EL element can be obtained. Because.

  The resin film listed above may be an unstretched film or a stretched film.

  The resin film according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Further, in the resin film substrate according to the present invention, surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. before forming the gas barrier film or polymer film, etc. May be performed.

  As the resin film, a long product wound up in a roll shape is convenient. The thickness of the resin film varies depending on the use of the resulting gas barrier film, so it cannot be specified unconditionally. However, when the gas barrier film is used as a packaging application, there is no particular limitation, and due to its suitability as a packaging material. 3 to 400 [mu] m, preferably 6 to 30 [mu] m.

  Moreover, 10-200 micrometers is preferable as a film thickness of the resin film used for this invention, More preferably, it is 50-100 micrometers.

In the gas barrier film according to the present invention, the water vapor transmission rate measured according to JIS K7129 is used as the water vapor transmission rate when it is used for an application requiring high water vapor barrier properties such as an organic EL display or a high-definition color liquid crystal display. It is preferably 0.01 g / m ² / day (40 ° C., 90% RH) or less, more preferably 1 × 10 ⁻³ g / m ² / day or less, and for organic EL display applications. Even if it is extremely small, a growing dark spot may be generated, and the display life of the display may be extremely shortened. Therefore, the water vapor transmission rate defined in JISK 7129 is 1 × 10 ⁻⁵ g / m ^2. / Day).

<Plasma CVD method>
In the method for producing a gas barrier film of the present invention, a plasma CVD method is used for forming a gas barrier thin film.

  The plasma CVD method is also called a plasma-assisted chemical vapor deposition method or PECVD method, and various inorganic substances can be applied in a three-dimensional form with good coverage and adhesion, and without increasing the substrate temperature too much. This is a technique capable of forming a film.

  In ordinary CVD (chemical vapor deposition), volatile and sublimated organometallic compounds adhere to the surface of a high-temperature substrate, causing a decomposition reaction due to heat, producing a thermally stable inorganic thin film. That's it. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and cannot be used for forming a film on a plastic substrate.

  On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) where a gas in a plasma state exists, and a volatilized / sublimated organometallic compound is introduced into the plasma space. The inorganic thin film is formed by spraying on the base material after the decomposition reaction occurs. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of a substrate on which an inorganic material is formed and can sufficiently form a film on a plastic substrate.

  However, in the normal plasma CVD method, it is necessary to apply an electric field to the gas to ionize it to be in a plasma state, and therefore, normally, the film was formed in a reduced pressure space of about 0.101 kPa to 10.1 kPa. When forming a film with a large area, the equipment is large and the operation is complicated, and in the present invention, in particular, the raw material gas and the discharge gas for forming a gas barrier thin film in the discharge space under atmospheric pressure or a pressure in the vicinity thereof are used. A thin film forming gas is supplied, a high frequency electric field is applied to the discharge space to excite the gas, and the resin film is exposed to the excited gas to form a gas barrier thin film on the transparent resin film It is preferable to apply the atmospheric pressure plasma method.

  Hereinafter, the atmospheric pressure plasma method according to the present invention will be described.

  As an atmospheric pressure plasma method for forming a laminated film such as an adhesion film, a ceramic film or a protective film according to the present invention or forming the polymer film by plasma polymerization, JP-A-10-154598 and JP-A-2003-2003 The thin film forming method described in Japanese Patent No. 49272, the pamphlet of WO 02/048428, etc. can be used, but the thin film forming method described in Japanese Patent Application Laid-Open No. 2004-68143 is a dense compressive stress with high gas barrier properties. It is preferable to form a ceramic film having a small thickness, whereby the formation of a polymer film by plasma polymerization or adhesion on a resin substrate by selecting the thin film forming gas as described above and adjusting the formation conditions respectively. A gas barrier layer such as a film, a ceramic film, or a protective film can be formed. Moreover, a web-like base material is drawn out from a roll-like original winding, and these can be continuously formed.

  The above atmospheric pressure plasma method according to the present invention is performed under atmospheric pressure or a pressure in the vicinity thereof. The atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and the good effects described in the present invention are obtained. In order to obtain, 93 kPa-104 kPa are preferable.

  The discharge condition in the present invention is that two or more electric fields having different frequencies are applied to the discharge space, and a method of applying an electric field in which the first high-frequency electric field and the second high-frequency electric field are superimposed is preferable.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the strength IV of the discharge start electric field IV. Relationship with
V1 ≧ IV> V2
Alternatively, it is preferable that V1> IV ≧ V2 is satisfied and the output density of the second high-frequency electric field is 1 W / cm ² or more.

  High frequency refers to one having a frequency of at least 0.5 kHz.

  When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

  In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (such as electrode configuration) and reaction conditions (such as gas conditions) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

  By applying a high-frequency electric field as described above to the discharge space, it is presumed that a discharge capable of forming a thin film is generated and high-density plasma necessary for forming a high-quality thin film can be generated.

  What is important here is that such a high-frequency electric field is applied between the opposing electrodes, that is, applied to the same discharge space. As in JP-A-11-16696, a method of applying two high-frequency electric fields to two different discharge spaces in which two application electrodes are arranged side by side is not preferable.

  Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one of them may be a continuous wave and the other may be a pulse wave. Further, a third electric field having a different frequency may be included.

  As a specific method for applying the high-frequency electric field of the present invention to the same discharge space, for example, the first high-frequency electric field having the frequency ω1 and the electric field strength V1 is applied to the first electrode constituting the counter electrode. An atmospheric pressure plasma discharge processing apparatus in which a first power source is connected and a second power source for applying a second high-frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode is used.

  The atmospheric pressure plasma discharge treatment apparatus includes a gas supply unit that supplies a discharge gas and a thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

  Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher electric field strength than the second power source.

  Here, the applied electric field strength and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of applied electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode portion, and an output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the applied electric field strength measurement.

  Note that the measurement position of the electric field intensity by the high-frequency voltage probe and oscilloscope used for the measurement is shown in FIG. 4 described later.

  By adopting the discharge conditions specified in the present invention, even a discharge gas having a high discharge starting electric field strength, such as nitrogen gas, can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. Can be done.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density with a high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film formation speed and an improvement in film quality can be achieved.

  As described above, the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and places the gas between the counter electrodes or between the electrodes. By exposing the substrate to be transferred to the plasma state gas, a thin film is formed on the substrate. As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrode. There is a jet type apparatus that blows out a plasma gas and exposes a substrate (which may be stationary or transferred) in the vicinity of the counter electrode to form a thin film on the substrate. .

  FIG. 10 is a schematic view showing an example of a jet type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

  In addition to the plasma discharge processing apparatus and the electric field applying means having two power supplies, the jet type atmospheric pressure plasma discharge processing apparatus is not shown in FIG. And an electrode temperature adjusting means.

  The atmospheric pressure plasma discharge treatment apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the frequency from the first power source 21 is from the first electrode 11 between the counter electrodes. A first high frequency electric field of ω1, electric field strength V1, and current I1 is applied, and a second high frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 22 is applied from the second electrode 12. It is like that. The first power supply 21 applies a higher high-frequency electric field strength (V1> V2) than the second power supply 22, and the first frequency ω1 of the first power supply 21 is lower than the second frequency ω2 of the second power supply 22. Apply frequency.

  A first filter 23 is installed between the first electrode 11 and the first power source 21 to facilitate passage of current from the first power source 21 to the first electrode 11, and current from the second power source 22. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.

  In addition, a second filter 24 is installed between the second electrode 12 and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode, and from the first power source 21. It is designed to ground the current and make it difficult to pass the current from the first power source 21 to the second power source.

  The aforementioned reactive gas G (thin film forming gas) is introduced into the space between the opposing electrodes (discharge space) 13 between the first electrode 11 and the second electrode 12 from a gas supply means as shown in FIG. While applying the above-described high-frequency electric field between the first electrode 11 and the second electrode 12 by the first power source 21 and the second power source 22 to generate discharge, the above-described reaction gas G (thin film forming gas) is in a plasma state. The substrate is blown out in the form of a jet below the counter electrode (at the bottom of the paper) to fill the processing space formed by the bottom surface of the counter electrode and the base material F with a gas G ° in a plasma state, A thin film is formed in the vicinity of the processing position 14 on the substrate F which is unwound from the unwinder) and conveyed. During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the substrate during the plasma discharge treatment, the physical properties and composition of the resulting thin film may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or longitudinal direction of the substrate does not occur as much as possible.

  FIG. 9 shows a measuring instrument and a measurement position used for measuring the applied electric field strength and the discharge starting electric field strength. Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.

  By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses in parallel with the transport direction of the base material F and simultaneously discharging gas in the same plasma state, it becomes possible to form a plurality of thin films at the same position, and for a short time. Thus, a desired film thickness can be formed. If a plurality of units are arranged in parallel with the conveying direction of the base material F, different thin film forming gases are supplied to each apparatus and different plasma state gases are jetted, it is also possible to form laminated thin films having different layers.

  FIG. 11 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus that treats a substrate between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge treatment apparatus according to the present invention is an apparatus having at least a plasma discharge treatment apparatus 300, an electric field application means 400 having two power supplies, a gas supply means 500, and an electrode temperature adjustment means 600.

  Between the counter electrodes 32 (hereinafter referred to as discharge between the counter electrodes) between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode group (second electrode) 36 (hereinafter, the square tube type fixed electrode group is referred to as a fixed electrode group). In this case, the base material F is plasma-discharged to form a thin film.

  In the discharge space 32 formed between the roll rotating electrode 35 and the fixed electrode group 36, the roll rotating electrode 35 receives a first high-frequency electric field of frequency ω1, electric field strength V1, current I1 from the first power source 41, and A second high-frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied to the fixed electrode group 36 from the second power source 42.

  A first filter 43 is installed between the roll rotation electrode 35 and the first power supply 41. The first filter 43 facilitates the passage of current from the first power supply 41 to the first electrode, and the second power supply. It is designed to ground the current from 42 and make it difficult to pass the current from the second power source 42 to the first power source. In addition, a second filter 44 is installed between the fixed electrode group 36 and the second power source 42, and the second filter 44 facilitates passage of current from the second power source 42 to the second electrode, It is designed to ground the current from the first power supply 41 and make it difficult to pass the current from the first power supply 41 to the second power supply.

  In the present invention, the roll rotation electrode 35 may be the second electrode, and the rectangular tube-shaped fixed electrode group 36 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The thin film forming gas G generated by the gas generator 51 of the gas supply means 500 is introduced into the plasma discharge processing vessel 31 from the air supply port 52 while the flow rate is controlled by a gas flow rate adjusting means (not shown).

  The substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed in the direction of the arrow from the previous process, and is accompanied by the nip roller 65 through the guide roller 64 and the substrate. And the like, and while being wound while being in contact with the roll rotating electrode 35, it is transferred to and from the rectangular tube fixed electrode group 36. At this time, the diameter of the guide roller 64 is 150 mm or more.

  An electric field is applied from both the roll rotating electrode 35 and the fixed electrode group 36 during the transfer, and discharge plasma is generated between the counter electrodes (discharge space) 32. The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 35.

  A plurality of rectangular tube-shaped fixed electrodes are provided along a circumference larger than the circumference of the roll electrode, and the discharge areas of the electrodes are all the corners facing the roll rotating electrode 35. It is represented by the sum of the areas of the surface of the cylindrical fixed electrode facing the roll rotation electrode 35.

  The base material F passes through the nip roller 66 and the guide roller 67 and is wound up by a winder (not shown) or transferred to the next process. At this time, the diameter of the guide roller 67 is 150 mm or more.

  Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.

  During the thin film formation, in order to heat or cool the roll rotating electrode 35 and the fixed electrode group 36, the medium whose temperature is adjusted by the electrode temperature adjusting means 600 is sent to both electrodes by the liquid feed pump P through the pipe 61, Adjust the temperature from Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

  FIG. 12 shows a plasma discharge having a rotating roll electrode and a rectangular tube electrode facing the roll electrode, and applying a first high frequency electric field and a second high frequency electric field with different frequencies superimposed between the electrodes. An example of a non-contact conveyance type plasma discharge processing apparatus having a processing step is shown.

  The base material F fed out from the roll-shaped base material winding is provided with a nip roller 200 and a partition plate 220 via a non-contact conveying device (floater) 14A designed to have respective curvature radii defined in the present invention. Then, it enters the discharge treatment chamber 31, is held by the rotating roll electrode 10A, is transferred in close contact, and is subjected to plasma discharge treatment in the discharge portion 100A formed between the opposing rectangular tube electrodes 10a ( The reactive gas G is supplied from the reactive gas supply unit 30A, and the processed gas G ′ is discharged from the discharge port 40A). After that, after exiting the discharge processing chamber through the nip roller 210 and the partition plate 230, the conveying direction is reversed by another non-contact conveying device (floater) 14B so that the processing surface does not come into contact with the reversing roller. Enter the discharge treatment chamber and receive treatment continuously. This apparatus shows a plasma discharge processing apparatus in which three discharge processing chambers 31 each including a rotating roll electrode and three rectangular tube-shaped electrodes facing each roll electrode are continuous. Of course, one or more square tube electrodes may be arranged in each discharge treatment chamber.

  In any case, the surfaces subjected to the plasma discharge treatment are non-contact by the non-contact conveying devices 14A to 14D that support the continuously running web by the gas being ejected from the outlet, and are curved surfaces defined in the present invention. In this example, plasma discharge treatment is performed in three discharge treatment chambers while the surface is conveyed along the surface.

  Via the last non-contact conveyance device (floater), the discharge treatment surface is non-contact, and the treated substrate F is transferred to a winding process and wound by a winder.

  Further, in this apparatus, the non-contact transfer device is provided immediately before the plasma discharge treatment, and is also used as a preheating means for avoiding deformation such as shrinkage of the base material due to a rapid temperature rise by the plasma discharge treatment. I can do it.

  As for the roll electrodes 10A, 10B, 10C and the rectangular tube type electrode shown in FIG. 12, a dielectric is coated on a conductive metallic base material as described above and as described in detail later. Has a structured.

  The distance between the facing roll electrode and the rectangular tube type electrode is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of performing uniform discharge as the distance between the dielectric surfaces.

  Here, three fixed electrodes (in this case, rectangular tube electrodes) are arranged along the circumference of the cylindrical electrode, but one or more may be provided. The discharge area of the electrode is represented by the sum of the areas of the surfaces of all the fixed electrodes facing the rotating roll electrode facing the roll electrode. The discharge area can be increased by installing a plurality.

  In addition, in order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the base material F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated, It is preferable to be able to adjust the temperature during discharge, and this is also the same.

  The plasma discharge apparatus in FIG. 12 performs a thin film formation or a surface modification process by performing a plasma discharge process on the substrate F in the discharge portions 100A to 100C formed between the roll electrodes and the rectangular tube type electrodes. is there.

  Each roll electrode is a first electrode, and a square tube electrode is a second electrode. Between the roll electrode 10A and the square tube electrode 10a, for example, the roll electrode 10A is supplied with frequency ω1, electric field strength V1, current from the first power source 91. A first high-frequency electric field of I1 is applied, and a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 is applied from the second power source 92 to the opposing rectangular tube electrode 10a.

  A first filter 93 is installed between the roll electrode 10A (first electrode) and the first power source 91, and the first filter 93 facilitates the passage of current from the first power source 91 to the first electrode. It is designed to ground the current from the second power source 92 and make it difficult to pass the current from the second power source 92 to the first power source. Further, a second filter 94 is installed between the opposing rectangular tube electrode 10a (second electrode) and the second power source 92, and the second filter 94 is connected from the second power source 92 to the second electrode. It is designed so that the current from the first power supply 91 is grounded and the current from the first power supply 91 to the second power supply is difficult to pass.

  Similarly, between the roll electrode 10B and the rectangular tube electrode 10b, and between the roll electrodes 10C and 10c, the roll electrode 10B and the roll electrode 10C are the first electrodes, and the rectangular tube electrodes 10b and 10c. Similarly, the first power source 91 and the filter 93 are connected to the second electrode, and the second power source 92 and the filter 94 are connected to the second electrode.

  FIG. 13 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIGS. 11 and 12 and the dielectric material coated thereon.

  In FIG. 13, a roll electrode 35a is formed by covering a conductive metallic base material 35A and a dielectric 35B thereon. In order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the substrate F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated.

  FIG. 14 is a perspective view showing an example of the structure of a conductive metallic base material of a rectangular tube type electrode and a dielectric material coated thereon.

  In FIG. 14, a rectangular tube electrode 36a has a coating of a dielectric 36B similar to that shown in FIG. 12 on a conductive metallic base material 36A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.

  The rectangular tube electrode 36a shown in FIG. 14 may be a cylindrical electrode, but the rectangular tube electrode has an effect of widening the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  13 and 14, a roll electrode 35a and a rectangular tube electrode 36a are formed by spraying ceramics as dielectrics 35B and 36B on conductive metallic base materials 35A and 36A, respectively, and then sealing a sealing material of an inorganic compound. Used and sealed. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metal base materials 35A and 36A include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  The distance between the first and second electrodes facing each other is the shortest distance between the surface of the dielectric and the surface of the conductive metal base material of the other electrode when a dielectric is provided on one of the electrodes. Say. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing 0.15 mm, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to obtain insulation. For example, in FIG. 13, it is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the base material surface) with the above-described material.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl industry 400kHz CF-2000-400k etc. can be mentioned, and all can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150 MHz CF-2000-150M and the like can be mentioned, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the opposing electrodes supplies electric power (power density) of 1 W / cm ² or more to the second electrode (second high frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in which discharge occurs between the electrodes.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

Electrodes coated with a dielectric material preferably have characteristics that match between various metal base materials and dielectric materials. One of the characteristics is the difference in the coefficient of linear thermal expansion between the metal base material and the dielectric material. Is a combination of 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic sprayed coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or a titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The metallic base material of the electrode useful for the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and are combined with a dielectric described later applied on the titanium alloy or titanium metal as a metallic base material. It can withstand the use at high temperature for a long time.

  On the other hand, as a required characteristic of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having such a void and a low void ratio include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire, or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. The plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, high adhesion strength and high density coating can be obtained. Specifically, reference can be made to a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferable specification that can withstand high power is that the dielectric thickness is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

  In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, a metal oxide is preferable, and among these, a compound containing silicon oxide (SiOx) as a main component is particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are sequentially repeated several times, mineralization is further improved and a dense electrode without deterioration can be obtained.

  In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed film using the metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid, the content of the metal oxide after curing is 60 It is preferably at least mol%. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the cured SiOx content (x is 2 or less) is preferably 60 mol% or more. The SiOx content after curing is measured by analyzing the tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

  In the electrode according to the thin film forming method of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the base material of the electrode may be adjusted to be 10 μm or less. From the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. In this way, the dielectric surface of the dielectric-coated electrode can be polished and the dielectric thickness and the gap between the electrodes can be kept constant, the discharge state can be stabilized, the heat shrinkage difference and Distortion and cracking due to residual stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such heat-resistant temperature can be applied within the range of the difference in linear thermal expansion coefficient between the metallic base material and the dielectric by applying a dielectric material provided with the above-mentioned ceramic spraying or layered glass lining with different amounts of mixed bubbles. This can be achieved by appropriately combining means for appropriately selecting materials.

<Application field of gas barrier film>
The gas barrier film having high water vapor and oxygen barrier properties according to the present invention can be used as various sealing materials and films.

  The gas barrier film according to the present invention can also be used for display elements such as organic EL elements. When used in an organic EL device, the gas barrier film of the present invention is transparent, and therefore, the gas barrier film can be used as a substrate to extract light from this side. That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin base material for an organic electroluminescence element. Then, using the ITO transparent conductive film provided on the substrate as an anode, an organic EL material layer including a light emitting layer is provided thereon, and further, a cathode made of a metal film is formed to form an organic EL element. The organic EL element layer can be sealed by stacking another sealing material (although it may be the same) and adhering the gas barrier film substrate to the surroundings and encapsulating the element. The influence on the element by gas can be sealed.

  In addition, the organic EL light emitting device has a problem of low light extraction efficiency. Therefore, it is preferable to have a structure for improving light extraction in combination with the use of these gas barrier films as a film substrate.

  Therefore, when the gas barrier film according to the present invention is used as a resin base material for an organic electroluminescence element, the surface has unevenness that diffracts or diffuses light in order to improve the light extraction efficiency from the organic EL element. It preferably has a shape.

  The gas barrier film according to the present invention can be applied to a sealing film.

  In the process of manufacturing organic EL, a transparent conductive film is formed on a ceramic film, and this is used as an anode, and an organic EL material layer constituting an organic EL element and a metal layer serving as a cathode are laminated thereon. Furthermore, another gas barrier film is used as a sealing film to be sealed by overlapping. As another sealing material (sealing film), a gas barrier film having a ceramic film having a dense structure according to the present invention can be used.

  The organic EL material using the gas-gas barrier film according to the present invention includes a display device and a display as well as various light emitting light sources and lighting devices, such as household lighting, interior lighting, and an exposure light source. In addition, it is also useful for display devices such as backlights of liquid crystal display devices. In addition, backlights for watches, signboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. There are a wide range of uses such as household appliances.

Example 1
The example which produced the gas-barrier film using the plasma discharge processing apparatus concerning the invention of Claims 1-6 is shown below.

  The plasma discharge treatment apparatus was processed using the apparatus shown in FIG. 2, and raw materials and electric power were supplied to each electrode part to form a thin film on the substrate as follows.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (80 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

The cylindrical electrode used had a diameter of 500 mm and a width of 500 mm, and the opposing square electrode had a discharge area of 500 cm ² . The nip roller was made of silicone rubber (JIS hardness 70) and had the same width as the cylindrical electrode and a diameter of 75 mm.

  The EPC sensor used was SLH20 manufactured by Nireco, an optical type.

  As the base film, an acrylic clear hard coat layer-attached PEN film (thickness 150 μm, width 500 mm, 150 m roll) is used, and on this base material, a thin film is formed in the following order: adhesion layer / ceramic layer / protective layer. Formed. Each film thickness is 10 nm for the adhesion layer and 50 nm for the ceramic layer and 50 nm for the protective layer. The substrate film holding temperature during film formation was 120 ° C.

  In the plasma discharge treatment, after winding, the role of the winder and unwinder is changed, the conveyance direction of the substrate is reversed and reciprocated, and the respective production conditions are changed as follows, and the thickness of each layer is changed to the thickness of each layer. The conveyance speed was adjusted so that the process was performed three times, and the adhesion layer, the ceramic layer, the protection layer, and the base film were sequentially laminated.

  The conditions for forming each layer (power of the high frequency side power supply, thin film forming gas) are as follows.

<Ceramic layer>
Discharge gas: N ₂ gas Reaction gas 1: Oxygen gas 5% of the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.1% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz changed at 10 W / cm ² <Adhesion layer>
Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas to the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.5% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
<Protect layer>
Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas to the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.5% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
About the gas barrier film obtained above,
The surface of the film samples at 10 m, 70 m, and 140 m after the start of the plasma treatment after the production was visually observed. Is obtained.

Further, the gas barrier performance was evaluated by the oxygen permeability measuring device OX-TRAN2 / 21 · L type and the water vapor permeability measuring device PERMATRAN-W3 / 33G type manufactured by Mocon, respectively. The water vapor barrier performance was 10 ⁻⁶ (g / M ² / day) and the oxygen barrier performance is on the order of 10 ⁻⁴ (ml / m ² / day), and a uniform gas barrier film was obtained in any sample.

Example 2
The example which produced the gas-barrier film using the plasma discharge processing apparatus concerning the invention of Claims 7-10 is shown below.

  The plasma discharge treatment apparatus shown in FIG. 5 was used, and each raw material and electric power were supplied to each electrode part, and a thin film was sequentially formed on the substrate as follows.

  Here, the dielectric was coated with 1 mm of one-sided ceramic-sprayed material with both opposing roll electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (80 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

  The roll electrode has a diameter of 500 mm and a width of 500 mm. The nip rollers 20 and 21 are made of silicone rubber (JIS hardness 70) and have the same width as the cylindrical electrode and a diameter of 100 mm.

  Moreover, as a non-contact conveying apparatus, it has a cylindrical shape with a cross section of 7/8 arc (diameter 500 mm), and has a structure in which a SUS-304 wire is wound at an appropriate pitch on the air discharge section on the surface. Using a roll with holes for compressed air supply at the fixed shafts at both ends of the roll, measure the pressure value of the compressed air with a tension meter and supply air to a pressure of about 1 kPa Then, the gap between the substrate surface and the roll surface was adjusted to 5 mm. Thereby, the floating state of the web was averaged along the outer peripheral surface, and the web was conveyed without contacting the roll.

  The substrate after film formation was discharged from the discharge treatment chamber through a compartment separating the discharge treatment chamber from the outside air, and then wound up by a winder.

  Further, an EPC sensor for preventing meandering was used as the plasma discharge processing apparatus. As the EPC sensor, SLH20 manufactured by Nireco Corp. of optical type was used, and torque control was directly performed by a winding shaft. The tension measurement directly monitored the output of the torque motor.

  As a base material, an acrylic clear hard coat layer-attached PEN film (thickness 150 μm, width 500 mm, 150 m roll) was set on the unwinding shaft, and the base material was fed out from the original winding roll. In the plasma discharge treatment apparatus having the plasma discharge treatment step shown in FIG. 5 on the substrate to be transferred as follows, the discharge layers 100A, 100B and 100C are used to form the adhesion layer / A ceramic layer / protective layer was formed and laminated in this order. The thickness was adjusted so that the adhesion layer was 10 nm, the ceramic layer was 50 nm, and the protection layer was 50 nm. The substrate holding temperature during film formation was 120 ° C.

  The conditions for forming each layer (power of the high frequency side power supply, thin film forming gas) are as follows.

<Ceramic layer>
Discharge gas: N ₂ gas Reaction gas 1: Oxygen gas 5% of the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.1% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz changed at 10 W / cm ² <Adhesion layer>
Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas to the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.5% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
<Protect layer>
Discharge gas: N ₂ gas Reaction gas 1: 1% of hydrogen gas to the total gas
Reaction gas 2: Tetraethoxysilane (TEOS) is 0.5% of the total gas
Low frequency side power supply power: 80 kHz, 10 W / cm ²
High frequency side power supply power: 13.56 MHz at 5 W / cm ²
About the gas barrier film obtained above,
The surface of the film samples at 10 m, 70 m, and 140 m after the start of the plasma treatment after the production was visually observed. Is obtained.

Further, the gas barrier performance was evaluated by the oxygen permeability measuring device OX-TRAN2 / 21 · L type and the water vapor permeability measuring device PERMATRAN-W3 / 33G type manufactured by Mocon, respectively. The water vapor barrier performance was 10 ⁻⁶ (g / M ² / day) and the oxygen barrier performance is on the order of 10 ⁻⁴ (ml / m ² / day), and a uniform gas barrier film was obtained in any sample.

  Hereinafter, the inventions described in claims 11 to 15 will be specifically described by Examples 3 to 5.

Example 3
<< Production of resin film >>
Using a PEN (polyethylene naphthalate) film (width 50 cm, thickness 125 μm) Q65 made by Teijin DuPont as a resin base material, a coating solution for actinic radiation curable resin layer having the following composition is prepared on this, and the film thickness after curing is The film was applied using a micro gravure coater so as to have a thickness of 6 μm, and the solvent was evaporated and dried, followed by curing with 0.2 J / cm ² of UV irradiation using a high pressure mercury lamp to form a polymer film composed of an acrylic cured layer.

(Coating liquid for active ray curable resin layer)
Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Dimethoxybenzophenone photoinitiator 4 parts by weight Methyl ethyl ketone 75 parts by weight Propylene Glycol monomethyl ether 75 parts by mass << Preparation of gas barrier film >>
[Preparation of Sample 1]
On the resin film having the polymer layer composed of the acrylic cured layer prepared as described above, an adhesion film (50 nm), a ceramic film (30 nm), a protective film (200 nm) and a thin film are sequentially formed under the following conditions. Sample 1 which is a gas barrier film was obtained by Manufacturing Method 1 to be performed.

  Sample 1 was produced by using a production line having three atmospheric pressure plasma discharge treatment apparatuses shown in FIG. 8 to continuously form an adhesion film, a ceramic film, and a protective film. At this time, as the guide rollers AR1 to AR7 for conveyance in contact with the surface (surface A) of the resin film, a guide roller having a core metal made of metal and coated on the surface with a resin having a diameter of 70 mm is used. As the guide rollers BR1 to BR3 for conveyance in contact with the surface B), guide rollers having a diameter of 40 mm whose core metal is made of metal and whose surface is coated with resin are used. The transport tension was controlled to 90 N / m.

  Moreover, atmospheric pressure plasma discharge processing apparatus CS1-CS3 was set to the following conditions using the atmospheric pressure plasma discharge processing apparatus of FIG.

(Adhesion film formation: CS1)
<Adhesion film; thin film forming gas composition>
Discharge gas: Nitrogen gas 94.85% by volume
Reactive gas: Hexamethyldisiloxane 0.15% by volume
Additive gas: Oxygen gas 5.0% by volume
<Adhesion film formation conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (Voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Ceramic film formation: CS2)
<Ceramic film; Thin film forming gas composition>
Discharge gas: Nitrogen gas 94.99 volume%
Reactive gas: Tetraethoxysilane 0.01% by volume
Additive gas: Oxygen gas 5.0% by volume
<Ceramic film deposition conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (Voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (Voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
(Protective film formation: CS3)
<Protective film; thin film forming gas composition>
Discharge gas: Nitrogen gas 94.5% by volume
Reactive gas: 0.5% by volume of hexamethyldisiloxane
Additive gas: Oxygen gas 5.0% by volume
<Protective film formation conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (Voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
[Preparation of Samples 2 to 12]
In the preparation of Sample 1, the diameters of the guide roller AR in contact with the surface (surface A) of the resin film and the guide roller BR in contact with the back surface (surface B) of the resin film were changed as shown in Table 1. Similarly, Samples 2 to 12 (Production Methods 2 to 12) were produced.

<< Evaluation of gas barrier film >>
The following evaluation was performed on each of the prepared samples.

(Measurement of water vapor transmission rate)
About each produced sample, the water-vapor-permeation rate was measured by the method described in JISK7129 (1992). In addition, the water vapor permeability measuring apparatus PERMATRAN-W 3/33 MG module manufactured by MOCON was used for the measurement (g / m ² / day (40 ° C. 90% RH)).

[Measurement of oxygen permeability]
About each produced sample, according to JISK7126 (1987), oxygen permeability was measured using the oxygen permeability measuring apparatus OX-TRAN 2/21 ML module by MOCON (ml / m < ² > / day / atm ( 22 ° C. 0% RH (Dry))).

[Evaluation of thin film uniformity]
For each sample prepared above, a sample having a width of 50 cm and a length of 10 cm was cut out, and the film thickness at 100 locations was measured at random using a thin film measuring apparatus F20-UV manufactured by FILMETRICS, and the maximum film thickness MAX and the minimum film were measured. The thickness MIN and the average film thickness AVE were obtained, and the film thickness variation rate (%) was measured according to the following formula, which was used as a measure of the thin film uniformity.

Film thickness fluctuation rate = (maximum film thickness MAX−minimum film thickness MIN) / average film thickness AVE × 100 (%)
The results obtained as described above are shown in Table 1.

  As is apparent from the results shown in Table 1, the sample produced by the production method in which the curvature radii of the surface A and the surface B of the sample to be continuously conveyed were set as the conditions defined in the present invention, the water vapor transmission rate compared to the comparative example. Further, it can be seen that the oxygen permeability is low and the gas barrier property is excellent.

Example 4
Samples 13 to 20 (Manufacturing methods 13 to 20) were prepared in the same manner except that the transport tension of the resin film was changed as shown in Table 2 in the preparation of Sample 9 (Manufacturing method 9) described in Example 3. Produced.

  Next, in the same manner as in the method described in Example 1, measurement of water vapor transmission rate and oxygen transmission rate and evaluation of thin film uniformity were performed, and the obtained results are shown in Table 2.

  As is clear from the results shown in Table 2, the gas barrier film produced by setting the transport tension in the range of 50 to 200 N / m can obtain a low water vapor transmission rate and oxygen transmission rate. It can be seen that the uniformity is excellent.

Example 5
In the preparation of each sample described in Example 3, a contactless transfer type atmospheric pressure plasma discharge treatment apparatus shown in FIG. 12 is used instead of the contact transfer type atmospheric pressure plasma discharge treatment apparatus shown in FIGS. 8 and 11. Each sample was prepared in the same manner except that the radius of curvature of the non-contact transfer device was changed under the same conditions as in Example 3, and the water vapor transmission rate was determined in the same manner as in the method described in Example 3. As a result of evaluating the oxygen transmission rate and the coating film uniformity, even in the non-contact conveyance method, the sample produced by the manufacturing method with the curvature radius of the surface A and the surface B of the sample to be continuously conveyed as defined in the present invention, Compared to the comparative example, it was confirmed that the water vapor transmission rate and the oxygen transmission rate were low and the gas barrier property was excellent.

Claims (15)

A plasma discharge treatment device that performs plasma discharge treatment on the surface of a substrate that is continuously transferred between a winder (winding shaft) and an unwinder (unwinding shaft) under atmospheric pressure or in the vicinity thereof, between the winder and the unwinder. In addition, at least one of the two electrodes formed of cylindrical electrodes, and at least two nip rollers using the cylindrical electrode as a backup roller, between the nip rollers, and between the two opposed electrodes are formed. Discharge unit, means for supplying a reaction gas at or near the atmospheric pressure provided in the discharge unit, means for discharging exhaust gas after treatment, and means for applying a voltage between the two opposed electrodes ,
Each having a plasma discharge treatment apparatus,
In the discharge part, the reaction gas is supplied from the means for supplying the reaction gas,
In the plasma discharge processing apparatus for applying a voltage between the two electrodes facing each other to generate a plasma discharge and performing a plasma discharge process on the surface of the substrate passing through the discharge part while being in contact with the cylindrical electrode,
A plasma discharge processing apparatus, wherein a roller that contacts the surface to be processed of the base material between the winder and the unwinder is constituted only by a nip roller on a cylindrical electrode. 2. The plasma discharge processing apparatus according to claim 1, wherein a cleaning roller is provided in contact with a portion outside the region constituting the discharge portion of the cylindrical electrode. 3. The plasma discharge processing apparatus according to claim 1, further comprising at least one EPC (edge position control) sensor. The winder and unwinder can play a role, and the substrate can be transferred in the reverse direction. By removing the wound substrate without removing it, the plasma discharge treatment is continuously performed in a reciprocating manner. The plasma discharge treatment apparatus according to any one of claims 1 to 3, wherein: The plasma discharge processing apparatus according to any one of claims 1 to 4, wherein torque control is directly performed in the winder and the unwinder. The plasma discharge treatment apparatus according to any one of claims 1 to 5, wherein a preheating zone of a base material is provided in front of the discharge unit. A plasma discharge treatment apparatus for performing plasma discharge treatment on the surface of a substrate to be continuously transferred under atmospheric pressure or a pressure in the vicinity thereof,
Having at least a pair of opposing electrodes and a discharge portion formed between the opposing electrodes;
The base material passes through the discharge part while being in contact with one electrode of the opposing electrode, and after being subjected to plasma discharge treatment in the discharge part, the other part of the opposing electrode is again provided to the discharge part. It is transferred while being in contact with the electrode, and has a folding transfer means for plasma discharge treatment,
A means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof between a base material that reciprocally passes through the discharge section and a means for discharging the exhaust gas after treatment;
And a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned. A plasma discharge treatment apparatus for performing plasma discharge treatment on the surface of a substrate to be continuously transferred under atmospheric pressure or a pressure in the vicinity thereof,
A plurality of discharge portions formed between a plurality of pairs of opposed electrodes and the respective opposed electrodes, wherein the substrate is in contact with one electrode of each of the opposed electrodes; After passing through the discharge portion, the plasma discharge treatment is performed, and then the discharge portion is transferred to the discharge portion while being in contact with the other electrode facing each other, and the folded transfer means for performing the plasma discharge treatment is provided. Each has
In each discharge part, between the base material that reciprocally passes through each discharge part, it has a means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof, and a means for discharging exhaust gas after treatment,
And it is a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned. A plasma discharge treatment apparatus for performing plasma discharge treatment on the surface of a substrate to be continuously transferred under atmospheric pressure or a pressure in the vicinity thereof,
Having a discharge part formed between a pair of opposing electrodes and the opposing electrodes;
The base material passes through the discharge part while being in contact with one electrode of the opposing electrode, and after being subjected to plasma discharge treatment in the discharge part, the other part of the opposing electrode is again provided to the discharge part. It is transferred while being in contact with the electrode, and has a folding transfer means for plasma discharge treatment,
A means for supplying a reaction gas at atmospheric pressure or a pressure in the vicinity thereof between a base material that reciprocally passes through the discharge section and a means for discharging the exhaust gas after treatment;
And a plasma discharge treatment apparatus having means for generating a plasma discharge by applying a voltage between the opposing electrodes,
The said discharge means is comprised with the non-contact conveyance apparatus which supports the web which drive | works continuously by ejecting gas from a blower outlet, The plasma discharge processing apparatus characterized by the above-mentioned. The plasma discharge treatment apparatus according to any one of claims 7 to 9, wherein the opposing electrodes are rotating roll electrodes. In a method for producing a gas barrier film, in which at least one gas barrier thin film is formed by a plasma CVD method on a resin film having a curvature and continuously conveyed, the surface A of the resin film having at least one gas barrier thin film is formed. A method for producing a gas barrier film, wherein the radius of curvature during conveyance is 75 mm or more, and the radius of curvature of a surface B opposite to the surface A across the resin film is 37.5 mm or more. 12. The method for producing a gas barrier film according to claim 11, wherein the gas barrier thin film comprises an adhesive film, a ceramic film, and a protective film from the resin film side. The method for producing a gas barrier film according to claim 11 or 12, wherein the ceramic film is formed of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, or a mixture thereof. . The plasma CVD method excites the gas by supplying a gas containing a gas barrier thin film forming gas and a discharge gas to the discharge space under an atmospheric pressure or a pressure near the atmospheric pressure, and applying a high-frequency electric field to the discharge space. The method according to any one of claims 11 to 13, wherein the gas barrier thin film is formed on the resin film by exposing the resin film to the excited gas. Of producing a gas barrier film. The gas barrier film according to any one of claims 11 to 14, wherein a transport tension when continuously transporting the resin film is 50 N / m or more and 200 N / m or less. Manufacturing method.